Long chain branched polypropylene via polymerization with aluminum vinyl transfer agent

ABSTRACT

The present disclosure provides the use of quinolinyldiamido transition metal complexes, an activator and a metal hydrocarbenyl chain transfer agent, such as an aluminum vinyl-transfer agent, to produce long chain branched propylene polymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 16/026,196, filed Jul.3, 2018 which is a: 1) continuation-in-part of U.S. Ser. No. 15/869,984,filed Jan. 12, 2018, which claims priority to and benefit of U.S. Ser.No. 62/464,933 filed Feb. 28, 2017, and 2) continuation-in-part of U.S.Ser. No. 15/629,586, filed Jun. 21, 2017, which claims priority to andbenefit of 62/357,033 filed Jun. 30 2016.

FIELD OF THE INVENTION

The present disclosure relates to the use of quinolinyldiamidotransition metal complexes and catalyst systems with an activator and ametal hydrocarbenyl chain transfer agent, such as an aluminumvinyl-transfer agent (AVTA), to produce long chain branchedpolypropylene.

BACKGROUND OF THE INVENTION

Polypropylene with high melt strength is useful for the production ofpolypropylene foams and blown films. Polypropylene resins produced usingconventional processes and catalyst systems are typically highly linearwith insufficient melt strength for, inter alia, polypropylene foams andblown films. Linear polypropylene can be crosslinked using peroxides,but this process is expensive and leads to polymer degradation or highlycrosslinked polymers that are too stiff and, accordingly, lackprocessability.

U.S. Pat. Nos. 9,315,593; 9,260,552; and US 2014/256,893 describe theproduction of polyolefins using pyridyldiamido catalysts in the presenceof chain-transfer agents that do not feature transferrable vinyl groups.

Macromolecules 2002, 35, 6760-6762 discloses propene polymerization withtetrakis(pentafluorophenyl)borate, 7-octenyldiisobutylaluminum, andracMe₂Si(2-Me-indenyl)₂ZrCl₂ or Ph₂C(cyclopentadienyl)(fluorenyl)ZrCl₂to produce polypropylene with octenyldiisobutylaluminum incorporated asa comonomer.

JP 2004-83773-A describes the preparation of polypropylene in thepresence of trialkenylaluminum using metallocene and Ziegler-Nattacatalysts.

Macromolecules 1995, 28, 437-443 describes the formation of isotacticpolypropylene containing vinyl end groups by the Ziegler-Natta catalyzedpolymerization of propylene in the presence of dialkenylzincs.

Macromolecules 2002, 35, 3838-3843 describes the formation of long-chainbranched polypropylene via the insertion of in situ formedvinyl-terminated polypropylene into growing polymer chains.

Macromolecules 2002, 35, 9586-9594 describes the formation of long-chainbranched copolymers of ethylene and alpha olefins via the insertion ofin situ formed vinyl-terminated polymer into growing polymer chains.

EP 2436703 A1 describes the production of comb architecture branch blockcopolymers in a process that uses dual catalysts and a zinc-basedpolymerizable chain shuttling agent.

WO 2007/035492 describes the production of long-chain branched andbranch block copolymers by polymerization of alkene monomers in thepresence of a zinc-based polymerizable shuttling agent.

WO 2016/102690 discloses a process for preparation of a branchedpolyolefin using a metal hydrocarbyl transfer agent.

US 2018/134827, a parent to this disclosure, discloses the use ofpyridyldiamido and/or quinolinyldiamido transition metal complexes andcatalyst systems with an activator and a metal hydrocarbenyl chaintransfer agent, such as an aluminum vinyl-transfer agent (AVTA), toproduce branched propylene polymers, preferably propylene-ethylenecopolymers or propylene-ethylene-diene monomer copolymers.

There is a need for new and improved processes for the polymerization ofolefins, in order to achieve polymer properties, such as long chainbranching, high melting point, high molecular weights, increasedconversion, increased comonomer incorporation, and/or altered comonomerdistribution.

SUMMARY OF THE INVENTION

The present disclosure relates to processes to produce branchedpropylene polymers comprising contacting monomer including propylenewith a catalyst system comprising an activator, a metal hydrocarbenylchain transfer agent, and a catalyst compound represented by Formula(I):

wherein:M is a group 3, 4, or 5 metal;J is a three-atom-length bridge between the quinoline and the amidonitrogen;X is an anionic leaving group;L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R², R³, R⁴, R⁵, and R⁶ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyls, halogen, and phosphino;n is 1 or 2:m is 0, 1, or 2n+m is not greater than 4; andany two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joinedto form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic ring, or unsubstituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings;any two X groups may be joined together to form a dianionic group;any two L groups may be joined together to form a bidentate Lewis base;andan X group may be joined to an L group to form a monoanionic bidentategroup.

The present disclosure further relates to catalyst systems comprisingactivator, transition metal catalyst complex represented by the Formula(I) above, and aluminum vinyl transfer agent represented by formula:Al(R′)_(3−v)(R″)_(v)wherein each R′ independently is a C₁-C₃₀ hydrocarbyl group; each R″,independently, is a C₄-C₂₀ hydrocarbenyl group having an end-vinylgroup; and v is from 0.1 to 3:

The present disclosure further relates to novel branched propylenepolymers. A propylene long-chain branched polymer which can be suitablefor applications like foaming, thermoforming, blow molding, film castingor the like, because of having good flow characteristics and high meltstrength. A branched propylene polymer can include from about 90 wt % orgreater propylene, wherein said branched propylene polymers: a) has ag′_(vis) of 0.97 or less; b) has strain hardening ratio of 1 or greater;c) has an Mw of 50,000 g/mol or more; and d) has a Mw/Mn of 4 or less.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph illustrating strain hardening ratio in the curve ofextensional viscosity as a function of time, according to oneembodiment.

FIG. 2 is a graph illustrating extensional viscosity of linear andbranched homopolypropylenes, according to one embodiment.

DETAILED DESCRIPTION

The present disclosure is directed to polymerization processes toproduce—olefin polymers such polypropylene polymers using transitionmetal complexes and catalyst systems that include the transition metalcomplexes. In at least one embodiment, polyolefin polymers can bebranched propylene polymers produced by contacting propylene, optionalmonomer with a catalyst system including at least one activator, atleast one metal hydrocarbenyl chain transfer agent, and at least onecatalyst compound. In another class of embodiments, the presentdisclosure relates to branched propylene polymer compositions, havingunique properties and rheology performance.

In at least one embodiment, processes and catalysts of the presentdisclosure provide catalyst efficiency greater than 50,000 g polymer/gcatalyst, and polyolefins, such as propylene polymer, having from about90 wt % or greater propylene, a g′_(vis) value of 0.97 or less, an Mn of10,000 g/mol or greater, an Mw of 50,000 g/mol or greater, and an Mw/Mnof 4 or less.

For the purposes of the present disclosure, the numbering scheme for thePeriodic Table Groups is used as described in CHEMICAL AND ENGINEERINGNEWS, 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an elementfrom group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst including W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. “Catalystefficiency” is a measure of the mass of product polymer (P) produced permass of catalyst (cat) used (gP/gcat). The mass of the catalyst is theweight of the pre-catalyst without including the weight of theactivator.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as including anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” is used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer including at least 50 mol %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer including at least 50 mol % propylene derivedunits, and so on. For the purposes of the present disclosure, ethyleneshall be considered an α-olefin.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity (PDI), is defined to be Mwdivided by Mn. Unless otherwise noted, all molecular weight units (e.g.,Mw, Mn, Mz) are g/mol.

Unless otherwise noted all melting points (Tm) are DSC second melt.

The following abbreviations may be used herein: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl. Pr ispropyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, cPR iscyclopropyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum. MAO is methylalumoxane, p-Me is para-methyl, Ph isphenyl, Bn is benzyl (i.e., CH₂Ph), THF (also referred to as thf) istetrahydrofuran, RT is room temperature (and is 23° C. unless otherwiseindicated), tol is toluene, EtOAc is ethyl acetate, Cy is cyclohexyl,AVTA is aluminum vinyl transfer agent, Cp is cyclopentadienyl, Cp* ispentamethyl cydopentadienyl, and Ind is indenyl, etc.

A “catalyst system” includes at least one catalyst compound and at leastone activator. When “catalyst system” is used to describe such thecatalyst compound/activator combination before activation, it means theunactivated catalyst complex (precatalyst) together with an activatorand, optionally, a co-activator. When it is used to describe thecombination after activation, it means the activated complex and theactivator or other charge-balancing moiety. The transition metalcompound may be neutral as in a precatalyst, or a charged species with acounter ion as in an activated catalyst system. For the purposes of thepresent disclosure, when catalyst systems are described as includingneutral stable forms of the components, it is well understood by one ofordinary skill in the art, that the ionic form of the component is theform that reacts with the monomers to produce polymers. A polymerizationcatalyst system is a catalyst system that can polymerize monomers topolymer.

In the description herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, catalyst compound or a transitionmetal compound, and these terms are used interchangeably. An “anionicligand” is a negatively charged ligand which donates one or more pairsof electrons to a metal ion. A “neutral donor ligand” is a neutrallycharged ligand which donates one or more pairs of electrons to a metalion.

A scavenger is a compound that is added to facilitate polymerization byscavenging impurities. Some scavengers may also act as activators andmay be referred to as co-activators. A co-activator, that is not ascavenger, may also be used in conjunction with an activator in order toform an active catalyst. In some embodiments a co-activator can bepre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

Except with respect to the term “substituted hydrocarbyl,” the term“substituted” means that at least one hydrogen atom has been replacedwith at least one non-hydrogen group, such as a hydrocarbyl group, aheteroatom, or a heteroatom containing group, such as halogen (such asBr, Cl, F or I) or at least one functional group such as —NR*₂, —OR*,—SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂. —SR*, —BR*₂, —SiR*₃, —GeR*₃,—SnR*₃, —PbR*₃, and the like, where each R* is independently ahydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or unsubstituted completely saturated, partiallyunsaturated, or aromatic cyclic or polycyclic ring structure, or whereat least one heteroatom has been inserted within a hydrocarbyl ring. Asexamples, methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group, and ethyl alcohol is an ethyl group substituted with an—OH group. The term “substituted hydrocarbyl” means hydrocarbyl radicalsin which at least one hydrogen atom of the hydrocarbyl radical has beensubstituted with a heteroatom or heteroatom-containing group, such ashalogen (e.g., Br, Cl, F or I), or at least one functional group such as—NR*₂, —OR*, —SeR*, —TeR*, —PR*2, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃,—GeR*₃, —SnR*₃, —PbR*₃, and the like, where each R* is independently ahydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or unsubstituted completely saturated, partiallyunsaturated, or aromatic cyclic or polycyclic ring structure, or whereat least one heteroatom has been inserted within a hydrocarbyl ring.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,” areused interchangeably throughout this document. Likewise, the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic,and when cyclic, aromatic or non-aromatic. Examples of such radicals caninclude methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like includingtheir substituted analogues.

The terms “alkyl radical,” and “alkyl” are used interchangeablythroughout this disclosure. For purposes of this disclosure, “alkylradical” is defined to be C₁-C₁₀₀ alkyls that may be linear, branched,or cyclic. Examples of such radicals can include methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl,iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclooctyl, and the like including their substituted analogues.Substituted alkyl radicals are radicals in which at least one hydrogenatom of the alkyl radical has been substituted with at least anon-hydrogen group, such as a hydrocarbyl group, a heteroatom, or aheteroatom containing group, such as halogen (such as Br, Cl, F or I) orat least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂,—AsR*₂, —SbR*₂, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*,—SnR*3, —PbR*3, and the like, or where at least one heteroatom has beeninserted within a hydrocarbyl ring.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more double bonds. These alkenylradicals may be optionally substituted. Examples of suitable alkenylradicals can include ethenyl, propenyl, allyl, 1,4-butadienylcyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl,and the like, including their substituted analogues.

The term “alkoxy” or “alkoxide” means an alkyl ether or aryl etherradical where the term alkyl is as defined above. For purposes of thepresent disclosure, “alkoxides” include those where the alkyl group is aC₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain, branched,or cyclic. The alkyl group may be saturated or unsaturated. In someembodiments, the alkyl group may include at least one aromatic group.Examples of suitable alkyl ether radicals can include methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxyl, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl,4-bromo-xylyl. Likewise, heteroaryl means an aryl group where a ringcarbon atom (or two or three ring carbon atoms) has been replaced with aheteroatom, such as N, O, or S. As used herein, the term “aromatic” alsorefers to pseudoaromatic heterocycles which are heterocyclicsubstituents that have similar properties and structures (nearly planar)to aromatic heterocyclic ligands, but are not by definition aromatic;likewise the term aromatic also refers to substituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist(e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to onemember of the group (e.g., n-butyl) shall expressly disclose theremaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in thefamily. Likewise, reference to an alkyl, alkenyl, alkoxide, or arylgroup without specifying a particular isomer (e.g., butyl) expresslydiscloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, andtert-butyl).

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is aheteroatom-substituted ring.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn until thepolymerization is stopped.

The present disclosure relates to catalyst systems including aquinolinyldiamide transition metal complex represented by formula (I) or(II) described herein, an activator (such as an alumoxane or anon-coordinating anion), and metal hydrocarbenyl transfer agentrepresented by the formula: Al(R′)_(3−v)(R″)_(v), where each R′,independently, is a C₁ to C₃₀ hydrocarbyl group; each R″, independently,is a C₄ to C₂₀ hydrocarbenyl group having an allyl chain end; v is from0.1 to 3 (such as 1 or 2). For example, the metal hydrocarbenyl transferagent is an aluminum vinyl-transfer agent (AVTA) represented by theformula (A):Al(R′)_(3−v)(R″)_(v)where R″ is a hydrocarbenyl group containing 4 to 20 carbon atoms havingan allyl chain end, R′ is a hydrocarbyl group containing 1 to 30 carbonatoms, and v is 0.1 to 3, alternately 1 to 3, alternately 1.1 to lessthan 3, alternately v is 0.5 to 2.9, 1.1 to 2.9, alternately 1.5 to 2.7,alternately 1.5 to 2.5, alternately 1.8 to 2.2. The compoundsrepresented by the formula Al(R′)_(3−v)(R″)_(v) can be a neutralspecies, but anionic formulations may be envisioned, such as thoserepresented by formula (B): [Al(R′)_(4-w)(R″)_(w)]—, where w is 0.1 to4, R″ is a hydrocarbenyl group containing 4 to 20 carbon atoms having anallyl chain end, and R′ is a hydrocarbyl group containing 1 to 30 carbonatoms.

In at least one embodiment of any formula for a metal hydrocarbenyltransfer agent, such as formula A or B, described herein, each R′ isindependently chosen from C₁ to C₃ hydrocarbyl groups (such as a C₁ toC₂₀ alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecenyl, or an isomer thereof),and R″ is represented by the formula:—(CH₂)_(n)CH═CH₂where n is an integer from 2 to 18, such as 6 to 18, such as 6 to 12,such as 6 to 8, such as 6, or such as 8.

The catalyst/activator combinations are formed by combining thetransition metal complex with activators, including by supporting themfor use in slurry or gas phase polymerization. The catalyst/activatorcombinations may also be added to or generated in solutionpolymerization or bulk polymerization (in the monomer). The metalhydrocarbenyl transfer agent (such as an aluminum vinyl transfer agent)may be added to the catalyst and or activator before, during or afterthe activation of the catalyst complex or before or duringpolymerization. The metal hydrocarbenyl transfer agent (such as aluminumvinyl-transfer agent) is added to the polymerization reactionseparately, such as before, the catalyst/activator pair.

In at least one embodiment, the polymer produced from the polymerizationusing the catalyst systems described herein contains at least one vinylchain end. In at least one embodiment, polymers produced from thepolymerization can be propylene polymers and copolymers products. If thecatalyst complex chosen is also capable of incorporating bulky alkenemonomers, such as C₆ to C₂ alpha olefins, into the growing polymerchain, then the resulting polymer (such as an propylene copolymer) maycontain long chain branches formed by the insertion of a vinylterminated polymer chain formed in situ (also referred to as a“vinyl-terminated macromonomer”) into the growing polymer chains.Process conditions including residence time, the ratio of monomer topolymer in the reactor, and the ratio of transfer agent to polymer willaffect the amount of long chain branching in the polymer, the averagelength of branches, and the type of branching observed. A variety ofbranching types may be formed, which include comb architectures andbranch on branch structures similar to those found in low-densitypolyethylene. The combination of chain growth and vinyl-group insertionmay lead to polymer with a branched structure and having one or fewervinyl unsaturations per polymer molecule. The absence of significantquantities of individual polymer molecules containing greater than onevinyl unsaturation prevents or reduces the formation of unwantedcrosslinked polymers. For example, polymers having long chain branchingcan have a branching index (g′_(vis)) of 0.97 or less, alternately 0.95or less, alternately 0.90 or less, alternately 0.85 or less, alternately0.80 or less, alternately 0.75 or less, alternately 0.70 or less,alternately 0.60 or less.

If the catalyst chosen is poor at incorporating comonomers such as C₄ toC₂₀ alpha olefins, then the polymer obtained is largely linear (littleor no long chain branching). Likewise, process conditions including theratio of transfer agent to polymer will affect the molecular weight ofthe polymer. For example, polymers having little or no long chainbranching can have a g_(vis) of, more than 0.97, preferably 0.98 ormore.

Alkene polymerizations and co-polymerizations using one or more transferagents, such as an AVTA, with two or more catalysts are also ofpotential use. Desirable products that may be accessed with thisapproach includes polymers that have branch block structures and/or highlevels of long-chain branching.

The transfer agent to catalyst complex equivalence ratio can be fromabout 1:100 to 500,000:1. For example, the molar ratio of transfer agentto catalyst complex can be greater than one. Alternately, the molarratio of transfer agent to catalyst complex can be greater than 30. TheAVTA to catalyst complex equivalence ratio can be from about 1:100 to500,000:1. For example, the molar ratio of AVTA to catalyst complex canbe greater than one, such as the molar ratio of AVTA to catalyst complexis greater than 30.

The AVTA can also be used in combination with other chain transferagents such as scavengers, such as trialkyl aluminum compounds (wherethe alkyl groups are selected from C₁ to C₂₀ alkyl groups, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, or an isomer thereof). In at least oneembodiment, the AVTA can be used in combination with a trialkyl aluminumcompound such as TNOAL and TIBAL.

The transfer agent can also be used in combination withoxygen-containing organoaluminums such as bis(diisobutylaluminum)oxide,MAO, MMAO-3A, and other alumoxanes. Certain of these oxygen-containingorganoaluminums are expected to serve as scavengers while remainingsignificantly less prone to hydrocarbyl group chain-transfer than commonorganoaluminums, such as trimethylaluminum or TNOAL.

The production of di-end-functionalized polymers is possible with thistechnology. One product prior to exposure to air, from an alkenepolymerization performed in the presence of AVTA is the aluminum-cappedspecies Al(R′)_(3−v)(polymer-CH═CH₂)_(v), where v is 0.1 to 3(alternately 1 to 3, alternately 1, 2, or 3). The Al-carbon bonds willreact with a variety of electrophiles (and other reagents), such asoxygen, halogens, carbon dioxide, and the like. Thus, quenching thereactive polymer mixture with an electrophile prior to exposure toatmosphere would yield a di-end-functionalized product of the generalformula: Z-(monomers)_(n)-CH═CH₂, where Z is a group from the reactionwith the electrophile and n is an integer, such as from 1 to 1,000,000,alternately from 2 to 50,000, alternately from 10 to 25,000. Forexample, quenching with oxygen yields a polymer functionalized at oneend with a hydroxy group and at the other end with a vinyl group.Quenching with bromine yields a polymer functionalized at one end with aBr group and at the other end with a vinyl group.

Suitable metal hydrocarbenyl transfer agents (such as aluminum vinyltransfer agents) can be present at from 10 or 20 or 50 or 100equivalents to 600 or 700 or 800 or 1000 equivalents relative to thecatalyst complex. Alternately, the metal hydrocarbenyl transfer agentscan be present at a catalyst complex-to-transfer agent molar ratio offrom about 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively1:50 to 1:1; alternatively 1:10 to 1:1.

In at least one embodiment of the present disclosure, the aluminum vinyltransfer agent can be present at a catalyst complex-to-aluminum vinyltransfer agent molar ratio of from about 1:3000 to 10:1; alternatively1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1;alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; alternatively1:10 to 1:1, alternately from 1:1000 or more.

Transition Metal Complexes

Transition metal complexes for polymerization processes can include anyolefin polymerization catalyst that readily undergoes reversiblepolymeryl group chain transfer with the added aluminum vinyl transferagent (AVTA) and is also capable of incorporating the vinyl group of theAVTA to form a long-chain branched polymer. Suitable catalyst componentsmay include “non-metallocene complexes” that are defined to betransition metal complexes that do not feature a cyclopentadienyl anionor substituted cyclopentadienyl anion donors (e.g., cyclopentadienyl,fluorenyl, indenyl, such as methylcyclopentadienyl). Examples offamilies of non-metallocene complexes that may be suitable can includelate transition metal pyridylbisimines (e.g., U.S. Pat. No. 7,087,686),group 4 pyridyldiamidos (e.g., U.S. Pat. No. 7,973,116),quinolinyldiamidos (e.g., US 2018/0002352 A1), pyridylamidos (e.g., U.S.Pat. No. 7,087,690), phenoxyimines (e.g., Accounts of Chemical Research2009, 42, 1532-1544), and bridged bi-aromatic complexes (e.g., U.S. Pat.No. 7,091,292).

Non-metallocene complexes can include iron complexes of tridentatepyridylbisimine ligands, zirconium and hafnium complexes of pyridylamidoligands, zirconium and hafnium complexes of tridentate pyridyldiamidoligands, zirconium and hafnium complexes of tridentate quinolinyldiamidoligands, zirconium and hafnium complexes of bidentate phenoxyimineligands, and zirconium and hafnium complexes of bridged bi-aromaticligands.

Suitable non-metallocene complexes can include zirconium and hafniumnon-metallocene complexes. In at least one embodiment, non-metallocenecomplexes for the present disclosure include group 4 non-metallocenecomplexes including two anionic donor atoms and one or two neutral donoratoms. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic amidodonor. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic aryloxidedonor atom. Suitable non-metallocene complexes for the presentdisclosure include group 4 non-metallocene complexes including twoanionic aryloxide donor atoms and two additional neutral donor atoms.

Transition metal complexes suitable for these polymerization processescan include quinolinyldiamido transition metal complexes where athree-atom linker is used between the quinoline and the nitrogen donorin the 2-position of the quinoline ring. This has been found to be animportant aspect because the use of the three-atom linker is believed toyield a metal complex with a seven-membered chelate ring that is notcoplanar with the other five-membered chelate ring. The resultingcomplex is thought to be effectively chiral (C₁ symmetry), even whenthere are no permanent stereocenters present. This is a desirablecatalyst feature, for example, for the production of isotacticpolyolefins.

Transition metal complexes useful herein include quinolinyldiamidotransition metal complexes represented by Formula (I), such as byFormula (II):

wherein:M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (such as a group 4metal);J is group including a three-atom-length bridge between the quinolineand the amido nitrogen, such as a group containing up to 50 non-hydrogenatoms:E is carbon, silicon, or germanium;X is an anionic leaving group, (such as a hydrocarbyl group or ahalogen):L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R², R³, R⁴, R⁵, and R⁶ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyls, halogen, and phosphino;R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently selected from hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, or any two adjacent R groups are joined to form a substitutedor unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7, or 8 ring atoms and where substitutions on the ring can join toform additional rings;n is 1 or 2;m is 0, 1, or 2, wheren+m is not greater than 4; andany two adjacent R groups (e.g., R¹ and R², R² and R³, etc.) may bejoined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic ring, or unsubstituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings;any two X groups may be joined together to form a dianionic group:any two L groups may be joined together to form a bidentate Lewis base;andany X group may be joined to an L group to form a monoanionic bidentategroup.

In at least one embodiment, M is a group 4 metal, such as titanium,zirconium or hafnium.

In at least one embodiment, J is an aromatic substituted orunsubstituted hydrocarbyl (such as a hydrocarbyl) having from 3 to 30non-hydrogen atoms, such as J is represented by the formula:

where R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² are as defined above, E is carbon,silicon, or germanium; and any two adjacent R groups (e.g., R⁷ and R⁸,R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, etc.) may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms (such as 5 or 6 atoms), and said ringmay be saturated or unsaturated (such as partially unsaturated oraromatic), such as J is an arylalkyl (such as arylmethyl, etc.) ordihydro-1H-indenyl, or tetrahydronaphthalenyl group.

In at least one embodiment of the present disclosure, J is selected fromthe following structures:

where

indicates connection to the catalyst compound.

In at least one embodiment of the present disclosure. R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, and trimethylsilyl.

In at least one embodiment of the present disclosure, E is carbon.

In at least one embodiment of the present disclosure, R⁷, R⁸, R⁹, andR¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl,isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy,and trimethylsilyl.

In at least one embodiment of the present disclosure, R², R³, R⁴, R⁵,and R⁶ are independently selected from hydrogen, hydrocarbyls, alkoxy,silyl, amino, substituted hydrocarbyls, and halogen.

In at least one embodiment of the present disclosure, each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide and each X is independentlyselected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl,butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido,diethylamido, dipropylamido, and diisopropylamido.

In at least one embodiment of the present disclosure, R¹ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R¹ 3 isphenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl,2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl,3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

In at least one embodiment of the present disclosure, J isdihydro-H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In at least one embodiment of the present disclosure. R¹ is2,6-diisopropylphenyl and R¹ 3 is a hydrocarbyl group containing 1, 2,3, 4, 5, 6, or 7 carbon atoms.

In at least one embodiment of the present disclosure, R¹⁰ and R¹¹ arejoined to form a six-membered ring with the joined R¹⁰R¹¹ group being—CH₂CH₂CH₂—.

In at least one embodiment of the present disclosure. R¹ and R¹³ may beindependently selected from phenyl groups that are variously substitutedwith between zero to five substituents that include F, Cl, Br, I, CF3,NO2, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment of the present disclosure, thequinolinyldiamido transition metal complex represented by the Formula(II) above where:

M is a group 4 metal (such as hafnium):

E is selected from carbon, silicon, or germanium (such as carbon);

X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide,iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;

L is an ether, amine, or thioether;

R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (such as aryl);

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyhydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyls, halogen, and phosphino;

n is 1 or 2;

m is 0, 1, or 2;

n+m is from 1 to 4; and

two X groups may be joined together to form a dianionic group;

two L groups may be joined together to form a bidentate Lewis base;

an X group may be joined to an L group to form a monoanionic bidentategroup;

R⁷ and R⁸ may be joined to form a ring (such as an aromatic ring, asix-membered aromatic ring with the joined R⁷R⁸ group being—CH═CHCH═CH—):

R₁₀ and R₁₁ may be joined to form a ring (such as a five-membered ringwith the joined R₁₀R₁₁ group being —CH₂CH₂—, a six-membered ring withthe joined R₁₀R₁₁ group being —CH₂CH₂CH₂—).

In at least one embodiment of Formula (I) and (II), R⁴, R³, and R⁶ areindependently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and where adjacent R groups (R⁴ and R⁵, and/or R⁵ and R⁶) maybe joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,unsubstituted heterocyclic ring or substituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings.

In at least one embodiment, of Formula (I) and (II), R⁷, R⁸, R⁹, and R¹⁰are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, andsilyl, and where adjacent R groups (R⁷ and R⁸, and/or R⁹ and R¹⁰) may bejoined to form a saturated, substituted hydrocarbyl, unsubstitutedhydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings.

In at least one embodiment of Formula (I) or (II). R² and R³ are each,independently, selected from the group consisting of hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R² and R³ may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R² and R³ may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In at least one embodiment of Formula (I) or (II). R¹¹ and R¹² are each,independently, selected from the group consisting of hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹¹ and R¹² may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In at least one embodiment of Formula (I) or (II), R¹ and R¹³ may beindependently selected from phenyl groups that are variously substitutedwith between zero to five substituents that include F, Cl, Br, I, CF₃,NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment of Formula (II), suitable R¹²-E-R¹¹ groupsinclude CH₂, C(CH₃)₂, Si(CH₃)₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂,Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl),where alkyl is a C₁ to C₄ alkyl group (such as C₁ to C₂₀ alkyl, such asone or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is aC₅ to C₄₀ aryl group (such as a C₆ to C₂₀ aryl group, such as phenyl orsubstituted phenyl, such as phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

For example, the R groups above and other R groups mentioned hereafter,contain from 1 to 30, such as 2 to 20 carbon atoms, especially from 6 to20 carbon atoms.

In at least one embodiment of the present disclosure, E is carbon andR¹² and R¹¹ are independently selected from phenyl groups that aresubstituted with 0, 1, 2, 3, 4, or 5 substituents selected from thegroup consisting of F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,hydrocarbyl, and substituted hydrocarbyl groups with from one to tencarbons.

In at least one embodiment of Formula (II), R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, and trimethylsilyl.

In at least one embodiment of the present disclosure of Formula (II),R⁷, R⁸, R⁹, and R¹⁰ are independently selected from hydrogen, methyl,ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy,ethoxy, phenoxy, and trimethylsilyl.

In at least one embodiment of Formula (I) or (II), R², R³, R⁴, R⁵, andR⁶ are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, andhalogen.

In at least one embodiment of Formula (I) or (II), each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide.

In at least one embodiment of Formula (I) or (II), each X isindependently selected from methyl, benzyl, trimethylsilyl, neopentyl,ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo,dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In at least one embodiment of Formula (I) or (II), R′ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In at least one embodiment of Formula (I) or (II), R¹⁵ is phenyl,2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl,2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl,3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl,4-dimethylaminophenyl, or 2-phenylphenyl.

In at least one embodiment described herein of Formula (II), where J isdihydro-1H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In at least one embodiment of Formula (I) or (H), R is2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3,4, 5, 6, or 7 carbon atoms.

Further description of quinolinyldiamido transition metal complexes andtheir preparation is found at US 2018/0002352, which is incorporated byreference herein.

Ligand Synthesis

The quinolinyldiamine ligands described herein are generally prepared inmultiple steps. The main step in the synthesis of the quinolinyldiamineligand is the carbon-carbon bond coupling step shown below in Scheme 1,where fragment 1 and fragment 2 are joined together in a transitionmetal mediated reaction. In the specific examples described herein thecoupling step involves the use of Pd(PPh₃)₄, but other transition metalcatalysts (e.g., Ni or Cu containing complexes) are also useful for thistype of coupling reaction. In the specific examples, the W* and Y*groups used were a boronic acid ester and a halide, respectively. Thischoice was suitable for the Pd-mediated coupling step, but other groupsmay also be useful for the coupling reaction. Other possible W* and Y*groups of interest include alkali metal (e.g., Li), alkaline earth metalhalide (e.g., MgBr), zinc halide (e.g., ZnCl), zincate, halide, andtriflate. In Scheme 1, R¹ through R¹³ and E are as described above.

One method for the preparation of transition metal quinolinyldiamidecomplexes is by reaction of the quinolinyldiamine ligand with a metalreactant containing anionic basic leaving groups. Suitable anionic basicleaving groups include dialkylamido, benzyl, phenyl, hydrido, andmethyl. In this reaction, the role of the basic leaving group is todeprotonate the quinolinyldiamine ligand. Suitable metal reactants forthis type of reaction include, but are not limited to, HfBn₄ (Bn=CH₂Ph),ZrBn₄, TiBn₄, ZrBn₂Cl₂(OEt₂), HfBn₂Cl₂(OEt₂)₂,Zr(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₂C₂(dimethoxyethane), Hf(NMe₂)₄,Zr(NMe₂)₄, and Hf(NEt₂)₄. In the specific examples of the presentdisclosure, Hf(NMe₂)₄ is reacted with a quinolinyldiamine ligand atelevated temperatures to form the quinolinyldiamide complex with theformation of two molar equivalents of dimethylamine, which is lost orremoved before the quinolinyldiamide complex is isolated.

A second method for the preparation of transition metalquinolinyldiamide complexes is by reaction of the quinolinyldiamineligand with an alkali metal or alkaline earth metal base (e.g., BuLi,EtMgBr) to deprotonate the ligand, followed by reaction with a metalhalide (e.g., HfCl₄, ZrCl₄).

Quinolinyldiamide (QDA) metal complexes that contain metal-halide,alkoxide, or amido leaving groups may be alkylated by reaction withorganolithium, Grignard, and organoaluminum reagents as shown in Scheme2. In the alkylation reaction the alkyl groups are transferred to theQDA metal center and the leaving groups are removed. In Scheme 2, R¹through R¹³ and E are as described above and X* is a halide, alkoxide,or dialkylamido leaving group. Suitable reagents for the alkylationreaction include, but are not limited to, MeLi, MeMgBr, Me₂Mg, AlMe₃,AiBu₃, AlOct₃, and PhCH2MgCl. For example, 2 to 20 molar equivalents ofthe alkylating reagent are added to the QDA complex. The alkylations aregenerally performed in ethereal or hydrocarbon solvents or solventmixtures at temperatures ranging from −80° C. to 70° C.

In at least one embodiment of the present disclosure, the transitionmetal complex is not a metallocene. A metallocene catalyst is defined asan organometallic compound with at least one π-bound cyclopentadienylmoiety (or substituted cyclopentadienyl moiety) and more frequently twoπ-bound cyclopentadienyl moieties or substituted cyclopentadienylmoieties.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.

After the complexes described above have been synthesized, catalystsystems may be formed by combining them with activators in any suitablemanner including by supporting them for use in slurry or gas phasepolymerization. The catalyst systems may also be added to or generatedin solution polymerization or bulk polymerization (in the monomer).Suitable catalyst system includes a complex as described above and anactivator such as alumoxane or a non-coordinating anion.

Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Activators can include alumoxanecompounds, modified alumoxane compounds, and ionizing anion precursorcompounds that abstract a reactive, σ-bound, metal ligand making themetal complex cationic and providing a charge-balancing non-coordinatingor weakly coordinating anion.

Alumoxane Activators

In at least one embodiment, alumoxane activators are utilized as anactivator in the catalyst system. Alumoxanes are generally oligomericcompounds containing —Al(R¹)—O-sub-units, where R¹ is an alkyl group.Examples of alumoxanes include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.Alkylalumoxanes and modified alkylalumoxanes are suitable as catalystactivators, particularly when the abstractable ligand is an alkyl,halide, alkoxide or amide. Mixtures of different alumoxanes and modifiedalumoxanes may also be used. Suitable visually clear methylalumoxane mayalso be used. A cloudy or gelled alumoxane can be filtered to produce aclear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584). Another useful alumoxane is solidpolymethylaluminoxane as described in U.S. Pat. Nos. 9,340,630;8,404,880; and 8,975,209. Aluminum alkyls are available as hydrocarbonsolutions from commercial sources. Methylalumoxane (“MAO”) is availablefrom Albemarle as a 30 wt % solution in toluene.

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of suitable activator at up to a5000-fold molar excess A/M over the catalyst compound (per metalcatalytic site). The minimum activator-to-catalyst-compound is a 1:1molar ratio. Alternate ranges include from 1:1 to 500:1, alternatelyfrom 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. For example, alumoxane ispresent at zero mole %, alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,such as less than 300:1, such as less than 100:1, such as less than 1:1.

Non-Coordinating Anion Activators

A non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the non-coordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon.

“Compatible” non-coordinating anions can be those which are not degradedto neutrality when the initially formed complex decomposes. Further, theanion might not transfer an anionic substituent or fragment to thecation so as to cause it to form a neutral transition metal compound anda neutral by-product from the anion. Non-coordinating anions can bethose that are compatible, stabilize the transition metal cation in thesense of balancing its ionic charge at +1, and yet retain sufficientlability to permit displacement during polymerization.

It is within the scope of the present disclosure to use a neutral orionic activator, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) borate, a tris perfluorophenyl boron metalloidprecursor or a tris perfluoronaphthyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459), or combination thereof. It is also within the scope ofthe present disclosure to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

The catalyst systems of the present disclosure can include at least onenon-coordinating anion (NCA) activator. In at least one embodiment,boron containing NCA activators represented by the formula below can beused:Z_(d) ⁺(A^(d-))where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen; (L-H) is a Bronsted acid; A^(d-) is a boron containingnon-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protonsor protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thebulky ligand metallocene containing transition metal catalyst precursor,resulting in a cationic transition metal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver,tropylium, carboniums, ferroceniums and mixtures, such as carboniums andferroceniums. Z_(d) ⁺ can be triphenyl carbonium. Reducible Lewis acidscan be any triaryl carbonium (where the aryl can be substituted orunsubstituted, such as those represented by the formula: (Ar₃C⁺), whereAr is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl), such as thereducible Lewis acids in formula (14) above as “Z” include thoserepresented by the formula: (Ph₃C), where Ph is a substituted orunsubstituted phenyl, such as substituted with C₁ to C₄₀ hydrocarbyls orsubstituted a C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls oraromatics or substituted C₁ to C₂₀ alkyls or aromatics, such as Z is atriphenylcarbonium.

When Z_(d) ⁺ is the activating cation (L-H)_(d) ⁺, it can be a Bronstedacid, capable of donating a proton to the transition metal catalyticprecursor resulting in a transition metal cation, including ammoniums,oxoniums, phosphoniums, silyliums, and mixtures thereof, such asammoniums of methylamine, aniline, dimethylamine, diethylamine,N-methylaniline, diphenylamine, trimethylamine, triethylamine,N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromoN,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums fromtriethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniumsfrom ethers such as dimethyl ether diethyl ether, tetrahydrofuran anddioxane, sulfoniums from thioethers, such as diethyl thioethers,tetrahydrothiophene, and mixtures thereof.

The anion component A^(d-) includes those having the formula[M^(k+)Q_(n)]^(d-) where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (suchas 1, 2, 3, or 4); n−k=d; M is an element selected from Group 13 of thePeriodic Table of the Elements, such as boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Each Q can be a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group,and such as each Q is a pentafluoryl aryl group. Examples of suitableA^(d-) also include diboron compounds as disclosed in U.S. Pat. No.5,447,895, which is fully incorporated herein by reference.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst are the compounds described as (andparticularly those specifically listed as) activators in U.S. Pat. No.8,658,556, which is incorporated by reference herein.

The ionic stoichiometric activator Z_(d) ⁺ (A^(d-)) can be one or moreof N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate, methyldioctadecylammoniumtetrakis(pentafluorophenyl)borate, or methyl-bis(hydrogenatedtallow)ammonium tetrakis(pentafluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” asused herein refers to anionic activators represented by the formula:

where:each R₁ is independently a halide, such as a fluoride;Ar is substituted or unsubstituted aryl group (such as a substituted orunsubstituted phenyl), such as substituted with C₁ to C₄₀ hydrocarbyls,such as C₁ to C₂₀ alkyls or aromatics; each R₂ is independently ahalide, a C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxygroup of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂ hydrocarbylor hydrocarbylsilyl group (such as R₂ is a fluoride or a perfluorinatedphenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂hydrocarbyl or hydrocarbylsilyl group (such as R₃ is a fluoride or a C₆perfluorinated aromatic hydrocarbyl group); where R₂ and R₃ can form oneor more saturated or unsaturated, substituted or unsubstituted rings(such as R₂ and R₃ form a perfluorinated phenyl ring); andL is a neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;where the anion has a molecular weight of greater than 1020 g/mol; andwhere at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

For example, (Ar₃C)_(d) ⁺ can be (Ph₃C)_(d) ⁺, where Ph is a substitutedor unsubstituted phenyl, such as substituted with C₁ to Cao hydrocarbylsor substituted C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls oraromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3 Vs, where Vs is the scaledvolume. Vs is the sum of the relative volumes of the constituent atoms,and is calculated from the molecular formula of the substituent usingthe following table of relative volumes. For fused rings, the Vs isdecreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

For a list of particularly useful Bulky activators please see U.S. Pat.No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen fromthe activators described in U.S. Pat. No. 6,211,105.

Exemplary activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, trimethylammoniumtetrakis(perfluorophenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate,1-4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In at least one embodiment, the activator includes a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator includes one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddi-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate (where alkyl ismethyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

Suitable activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternateranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1, alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, such as 1:1 to 5:1.

It is also within the scope of the present disclosure that the catalystcompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0 573 120 B1; WO94/07928; and WO 95/14044 which discuss the use of an alumoxane incombination with an ionizing activator).

Useful chain transfer agents can be alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₁₈ aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl,hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or anisomer thereof) or a combination thereof, such as diethyl zinc,methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Optional Scavengers or Co-Activators

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Metal Hydrocarbenyl Transfer Agents (Aluminum Vinyl Transfer Agents)

The catalyst systems described herein further include a metalhydrocarbenyl transfer agent (which is any group 12 or 13 metal agentthat contains at least one transferrable group that has an allyl chainend), such as an aluminum vinyl-transfer agent, also referred to as anAVTA, (which is any aluminum agent that contains at least onetransferrable group that has an allyl chain end). An allyl chain end isrepresented by the formula H₂C═CH—CH₂—. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” “terminal vinyl group,” and “vinyl terminated” are usedinterchangeably herein and refer to an allyl chain end. An allyl chainend is not a vinylidene chain end or a vinylene chain end. The number ofallyl chain ends, vinylidene chain ends, vinylene chain ends, and otherunsaturated chain ends is determined using ¹H NMR at 120° C. usingdeuterated tetrachloroethane as the solvent on an at least 250 MHz NMRspectrometer.

Useful transferable groups containing an allyl chain end are representedby the formula CH₂═CH—CH₂—R*, where R* represents a hydrocarbyl group ora substituted hydrocarbyl group, such as a C₁ to C₂₀ alkyl, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, or an isomer thereof.

In the catalyst system described herein, the catalyst undergoes alkylgroup transfer with the transfer agent, which enables the formation ofpolymer chains containing one or more allyl chain ends.

Useful transferable groups containing an allyl chain end also includethose represented by the formula CH₂═CH—CH₂—R* where R* represents ahydrocarbeneyl group or a substituted hydrocarbeneyl group, such as a C₁to C₂₀ alkylene, such as methylene (CH₂), ethylene [(CH₂)₂], propandiyl[(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl [(CH₂)₆],heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉], decandiyl[(CH₂)₁₀], undecandiyl [(CH₂₀)₁₁], dodecandiyl [(CH₂)₁₂], or an isomerthereof. Suitable transferable groups are non-substituted linearhydrocarbeneyl groups. For instance, at least one R** is a C₄-C₂₀hydrocarbenyl group.

The term “hydrocarbeneyl” refers to a hydrocarb-di-yl divalent group,such as a C₁ to C₂₀ alkylene (i.e., methylene (CH₂), ethylene [(CH₂)₂],propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl[(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉],decandiyl [(CH₂)₁₀], undecandiyl [(CH₂)₁₁], dodecandiyl [(CH₂)₁₂], andisomers thereof).

AVTA's are alkenylaluminum reagents capable of causing group exchangebetween the transition metal of the catalyst system (M™) and the metalof the AVTA (M^(AVTA)). The reverse reaction may also occur such thatthe polymeryl chain is transferred back to the transition metal of thecatalyst system. This reaction scheme is illustrated below:

where M™ is an active transition metal catalyst site and P is thepolymeryl chain, M^(AVTA) is the metal of the AVTA, and R is atransferable group containing an allyl chain end, such as a hydrocarbylgroup containing an allyl chain end, also called a hydrocarbenyl oralkenyl group.

Suitable catalyst systems of the present disclosure have high rates ofolefin propagation and negligible or no chain termination via betahydride elimination, beta methyl elimination, or chain transfer tomonomer relative to the rate of chain transfer to the AVTA or otherchain transfer agent, such as an aluminum alkyl, if present.Quinolinyldiamido catalyst complexes (see US 2018/0002352) and/or othercatalyst compounds (U.S. Pat. Nos. 7,973,116; 8,394,902; 8,674,040;8,710,163; 9,102,773; US 2014/0256893; US 2014/0316089; and US2015/0141601) activated with non-coordinating activators such asdimethylanilinium tetrakis(perfluorophenyl)borate and/ordimethylanilinium tetrakis(perfluoronaphthyl)borate are particularlyuseful in the catalyst systems of the present disclosure.

In at least one embodiment of the present disclosure, the catalystsystem includes an aluminum vinyl transfer agent, which is representedby the formula (A):Al(R′)_(3−v)(R″)_(v)where R′ is a hydrocarbyl group containing 1 to 30 carbon atoms, R″ is ahydrocarbenyl group containing 4 to 20 carbon atoms having an allylchain end, and v is 0.1 to 3, alternately 1 to 3, alternately 1.1 toless than 3, alternately v is 0.5 to 2.9, 1.1 to 2.9, alternately 1.5 to2.7, alternately 1.5 to 2.5, alternately 1.8 to 2.2. Suitable compoundsrepresented by the formula Al(R′)_(3−v)(R″), are neutral species, butanionic formulations may be envisioned, such as those represented byformula (B): [Al(R′)_(4-w)(R″)_(w)]⁻, where w is 0.1 to 4, R′ is ahydrocarbyl group containing 1 to 30 carbon atoms, and R″ is ahydrocarbenyl group containing 4 to 20 carbon atoms having an allylchain end.

In at least one embodiment of any formula for a metal hydrocarbenyltransfer agent, such as formula A or B, described herein, each R′ isindependently chosen from C₁ to C₃₀ hydrocarbyl groups (such as a C₁ toC₂₀ alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof),and R is represented by the formula:—(CH₂)_(n)CH═CH₂where n is an integer from 2 to 18, such as 6 to 18, such as 6 to 12,such as 6.

In at least one embodiment of the present disclosure, particularlyuseful AVTAs include, but are not limited to,tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminumdiisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-1-en-1-yl)aluminum,and the like. Mixtures of one or more AVTAs may also be used. In someembodiments of the present disclosure,isobutyl-di(oct-7-en-1-yl)-aluminum,isobutyl-di(dec-9-en-1-yl)-aluminum,isobutyl-di(non-8-en-1-yl)-aluminum,isobutyl-di(hept-6-en-1-yl)-aluminum are suitable.

Metal hydrocarbenyl transfer agents can include one or more oftri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, tri(dodec-11-en-1-yl)aluminum,dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum,dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum,diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum,diethyl(dec-9-en-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum,diisobutyl(dec-9-en-1-yl)aluminum, anddiisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum,ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum,isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum,methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum,butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, andisobutyl-di(dodec-11-en-1-yl)aluminum.

Aluminum vinyl transfer agents can include organoaluminum compoundreaction products between aluminum reagent (AlR₃) and an alkyl diene.Suitable alkyl dienes include those that have two “alpha olefins”, asdescribed above, at two termini of the carbon chain. The alkyl diene canbe a straight chain or branched alkyl chain and substituted orunsubstituted. Exemplary alkyl dienes include but are not limited to,for example, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene,1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene,1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene,1,20-heneicosadiene, etc. Exemplary aluminum reagents includetriisobutylaluminum, diisobutylaluminumhydride,isobutylaluminumdihydride and aluminum hydride (AlH₃).

In at least one embodiment, R″ is butenyl, pentenyl, heptenyl, octenylor decenyl, such as R″ is octenyl or decenyl. R′ can be methyl, ethyl,propyl, isobutyl, or butyl, such as R′ is isobutyl.

In at least one embodiment of the present disclosure, v is about 2, or vis 2.

In at least one embodiment, v is about 1, or v is 1, such as from about1 to about 2.

v can be an integer or a non-integer, such as v is from 1.1 to 2.9, suchas from about 1.5 to about 2.7, e.g., such as from about 1.6 to about2.4, such as from about 1.7 to about 2.4, such as from about 1.8 toabout 2.2, such as from about 1.9 to about 2.1 and all ranges therebetween.

In at least one embodiment of the present disclosure, R′ is isobutyl andeach R″ is octenyl or decenyl, such as R′ is isobutyl, each R″ isoctenyl or decenyl, and v is from 1.1 to 2.9, such as from about 1.5 toabout 2.7, e.g., such as from about 1.6 to about 2.4, such as from about1.7 to about 2.4, such as from about 1.8 to about 2.2, such as fromabout 1.9 to about 2.1.

The amount of v (the aluminum alkenyl) is described using the formulas:(3−v)+v=3, and Al(R′)_(3−v)(R″)_(v) where R″ is a hydrocarbenyl groupcontaining 4 to 20 carbon atoms having an allyl chain end, R′ is ahydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3(such as 1.1 to 3). This formulation represents the observed average oforganoaluminum species (as determined by ¹H NMR) present in a mixture,which may include any of Al(R′)₃, Al(R′)₂(R″), Al(R′)(R″)₂, and Al(R″)₃.¹H NMR spectroscopic studies are performed at room temperature using aBruker 400 MHz NMR. Data is collected using samples prepared bydissolving 10-20 mg the compound in 1 mL of C₆D₆. Samples are thenloaded into 5 mm NMR tubes for data collection. Data is recorded using amaximum pulse width of 45°, 8 seconds between pulses and signalaveraging either 8 or 16 transients. The spectra are normalized toprotonated tetrachloroethane in the C6D6. The chemical shifts (δ) arereported as relative to the residual protium in the deuterated solventat 7.15 ppm.

In still another aspect, the aluminum vinyl-transfer agent has less than50 wt % dimer present, based upon the weight of the AVTA, such as lessthan 40 wt %, such as less than 30 wt %, such as less than 20 wt %, suchas less than 15 wt %, such as less than 10 wt %, such as less than 5 wt%, such as less than 2 wt %, such as less than 1 wt %, such as 0 wt %dimer. Alternately dimer is present at from 0.1 to 50 wt %, alternately1 to 20 wt %, alternately at from 2 to 10 wt %. Dimer is the dimericproduct of the alkyl diene used in the preparation of the AVTA. Thedimer can be formed under certain reaction conditions, and is formedfrom the insertion of a molecule of diene into the Al—R bond of theAVTA, followed by beta-hydride elimination. For example, if the alkyldiene used is 1,7-octadiene, the dimer is7-methylenepentadeca-1,14-diene. Similarly, if the alkyl diene is1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

Useful compounds can be prepared by combining an aluminum reagent (suchas alkyl aluminum) having at least one secondary alkyl moiety (such astriisobutylaluminum) and/or at least one hydride, such as adialkylaluminum hydride, a monoalkylaluminum dihydride or aluminumtrihydride (aluminum hydride. AlH₃) with an alkyl diene and heating to atemperature that causes release of an alkylene byproduct. The use ofsolvent(s) is not required. However, non-polar solvents can be employed,such as, as hexane, pentane, toluene, benzene, xylenes, and the like, orcombinations thereof.

In at least one embodiment of the present disclosure, the AVTA is freeof coordinating polar solvents such as tetrahydrofuran and diethylether.

After the reaction is complete, solvent if, present can be removed andthe product can be used directly without further purification.

The AVTA to catalyst complex equivalence ratio can be from about 1:100to 500,000:1. For example, the molar ratio of AVTA to catalyst complexcan be greater than 5, alternately greater than 10, alternately greaterthan 15, alternately greater than 20, alternately greater than 25,alternately greater than 30.

In another embodiment of the present disclosure, the metal hydrocarbenyltransfer agent is an alumoxane formed from the hydrolysis of the AVTA.Alternatively, the alumoxane can be formed from the hydrolysis of theAVTA in combination with other aluminum alkyl(s). The alumoxanecomponent is an oligomeric compound which is not well characterized, butcan be represented by the general formula (R—Al—O)_(m) which is a cycliccompound, or may be R′(R—Al—O)_(m)—AlR′₂ which is a linear compoundwhere R′ is as defined above and at least one R′ is the same as R (asdefined above), and m is from about 4 to 25, such as with a range of 13to 25. In at least one embodiment, all R′ are R. An alumoxane isgenerally a mixture of both the linear and cyclic compounds.

In at least one embodiment of the present disclosure, the metalhydrocarbenyl chain transfer agent is represented by the formula:Al(R′)_(3−v)(R″)_(v) where each R′ independently is a C₁-C₃₀ hydrocarbylgroup, each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having anend-vinyl group, and v is from 0.1 to 3, such as each R″, independently,is a C₄-C₂₀ hydrocarbenyl group having an allyl chain end and v is from0.1 to 3, such as v=2.

Polymerization Processes

The present disclosure relates to polymerization processes where monomer(such as propylene), and optionally comonomer, are contacted with acatalyst system including an activator, a metal hydrocarbenyl chaintransfer agent, and a catalyst compound, as described above. Thecatalyst compound and activator may be combined in any order, and may becombined prior to contacting with the monomer.

Catalyst complexes are useful in polymerizing unsaturated monomersconventionally known to undergo coordination-catalyzed polymerizationsuch as solution, slurry, gas-phase, and high-pressure polymerization.Solution phase polymerizations are preferred and may be performed inbatch reactors or continuous stirred tank, plug flow, or loop reactors.

For purposes of the present disclosure, one or more reactors in seriesor in parallel may be used.

The complexes, activator, transfer agent, and, when required,co-activator, may be delivered as a solution or slurry, eitherseparately to the reactor, activated in-line just prior to the reactor,or pre-activated and pumped as an activated solution or slurry to thereactor. Polymerizations are carried out in either single reactoroperation, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to thefirst reaction and another component to other reactors. In at least oneembodiment, the complex is activated in the reactor in the presence ofolefin and transfer agent.

In at least one embodiment, the polymerization process is a continuousprocess performed in one or more continuous stirred tank reactors inseries or in parallel.

Polymerization processes of the present disclosure can includecontacting one or more alkene monomers with the complexes, activatorsand transfer agents described herein. For purpose of the presentdisclosure, alkenes are defined to include multi-alkenes (such asdialkenes) and alkenes having just one double bond. Polymerization maybe homogeneous (solution or bulk polymerization) or heterogeneous(slurry—in a liquid diluent, or gas phase—in a gaseous diluent). Chaintransfer agents that cause irreversible chain transfer, such ashydrogen, silanes, or certain metal alkyls, are called chain terminatingagents and may be used in the practice of the present disclosure.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. Commonly, a solutionpolymerization is homogeneous. A homogeneous polymerization is one wherethe polymer product is dissolved in the polymerization medium. Forexample, such systems can be not turbid as described in J. VladimirOliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 2000, Vol.29, p. 4627.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent as a solvent or diluent. Asmall fraction of inert solvent might be used as a carrier for catalystand scavenger. A bulk polymerization system contains less than 25 wt %of inert solvent or diluent, such as less than 10 wt %, such as lessthan 1 wt %, such as 0 wt %.

The present polymerization processes may be conducted under conditions,for instance, including a temperature of about 30° C. to about 200° C.,such as from 60° C. to 195° C., such as from 70° C. to 190° C., such asfrom 75° C. to 150° C., such as from 85° C. to 125° C. such as from 90°C. to 100° C., such as 95° C. Preferably the process is conducted at atemperature of (70° C. to 150° C., alternately 80° C. to 120° C.,alternately 90° C. to 100° C.). The process may be conducted at apressure of from 0.05 MPa to 1500 MPa. In at least one embodiment, thepressure is between 0.1 MPa and 40 MPa, or in another embodiment thepressure is between 1.7 MPa and 30 MPa, or in another embodiment,especially under supercritical conditions, the pressure is between 15MPa and 1500 MPa.

If branching (such as a g′_(vis) of less than 0.98, preferably 0.97 orless) is desired in the polymer product, then, among other things, onemay increase the concentration of the metal hydrocarbenyl transferagent, increase the temperature of the polymerization reaction, increasethe solids content in the polymerization reaction mass (i.e., increasethe solids content) or increase the residence time of thepolymerization. Likewise, if a more linear polymer is desired, then,among other things, one may reduce the concentration of the metalhydrocarbenyl transfer agent, reduce the temperature of thepolymerization reaction, reduce the solids content in the polymerizationreaction mass (i.e., increase the solids content) or reduce theresidence time of the polymerization.

For example, in a polymerization, the run time of the reaction is up to300 minutes, such as from about 5 minutes to 250 minutes, such as fromabout 10 minutes to 120 minutes.

In at least one embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of from 0.1 psig to 1,000 psig (0.0007 MPato 6.895 MPa), such as from 0.1 psig to 500 psig (0.007 MPa to 3.45MPa), such as 10 psig to 100 psig (0.069 MPa to 0.689 MPa).

In at least one embodiment, the efficiency of the catalyst compound isat least 1,000 gP/gCat, such as 5,000 gP/gCat or more, such as 10,000gP/gCat or more, such as 50,000 gP/gCat or more, such as 100,000 gP/gCator more, such as 200,000 gP/gCat or more.

In at least one embodiment, the conversion of olefin monomer is at least10%, based upon polymer yield and the weight of the monomer entering thereaction zone, such as 20% or more, such as 30% or more, such as 40% ormore, such as 50% or more, such as 80% or more.

In at least one embodiment, little or no alumoxane is used in theprocess to produce the polymers. For example, alumoxane is present atzero mol %, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal less than 500:1, such as less than 300:1,such as less than 100:1, such as less than 1:1.

In at least one embodiment, little or no scavenger is used in theprocess to produce the propylene-based polymer. For example, scavenger(such as tri alkyl aluminum) is present at zero mol %, alternately thescavenger is present at a molar ratio of scavenger metal to transitionmetal of less than 100:1, such as less than 50:1, such as less than15:1, such as less than 10:1.

Monomers

Monomers include substituted or unsubstituted C₃ to C₄₀ alpha olefins,such as C₃ to C₂₀ alpha olefins, such as C₃ to C₁₂ alpha olefins, suchas propylene, butene, pentene, hexene, heptene, octene, nonene, decene,undecene, dodecene and isomers thereof. In at least one embodiment, themonomer includes propylene and an optional comonomer including one ormore C₄ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups. In at least one embodiment, the monomerincludes propylene and an optional comonomer including one or more C₄ toC₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. TheC₄ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₄ toC₄₀ cyclic olefins may be strained or unstrained, monocyclic orpolycyclic, and may optionally include heteroatoms and/or one or morefunctional groups.

Exemplary C₃ to C₄₀ olefin monomers and optional comonomers includepropylene, butene, pentene, hexene, heptene, octene, nonene, decene,undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof,and isomers thereof, such as hexene, heptene, octene, nonene, decene,dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbornadiene, and their respectivehomologs and derivatives, such as norbornene, norbornadiene, anddicyclopentadiene.

In at least one embodiment, one or more dienes are present in thepolymer produced herein at up to 10 wt %, such as at 0.00001 wt % to 1.0wt %, such as 0.002 wt % to 0.5 wt %, such as 0.003 wt % to 0.2 wt %,based upon the total weight of the composition. In some embodiments, 500ppm or less of diene is added to the polymerization, such as 400 ppm orless, such as 300 ppm or less. In other embodiments, at least 50 ppm ofdiene is added to the polymerization, or 100 ppm or more, or 150 ppm ormore.

Diolefin monomers include any suitable hydrocarbon structure, such as C₄to C₃₀, having at least two unsaturated bonds, where at least two of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). The diolefinmonomers can be selected from alpha, omega-diene monomers (i.e.,di-vinyl monomers). The diolefin monomers can be linear di-vinylmonomers, such as those containing from 4 to 30 carbon atoms. Dienes caninclude butadiene, pentadiene, hexadiene, heptadiene, octadiene,nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene,tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, forexample dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Cyclic dienes can include cyclopentadiene,vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Where olefins are used that give rise to short chain branching, such aspropylene, the catalyst systems may, under appropriate conditions,generate stereoregular polymers or polymers having stereoregularsequences in the polymer chains.

In at least one embodiment, the catalyst systems described herein areused in any polymerization process described above to produce propylenepolymers or copolymers. In at least one embodiment, the catalyst systemsdescribed herein are used in any polymerization process described aboveto produce branched propylene polymers.

In at least one embodiment, ethylene can be used as a comonomer. In apreferred embodiment, the branched propylene polymer comprises less than1% ethylene, preferably less than 0.5% ethylene, preferably 0% ethylene.

Scavengers

In at least one embodiment, when using a catalyst system describedherein, a catalyst system will additionally include one or morescavenging compounds. Here, the term scavenging compound means acompound that removes polar impurities from the reaction environment.These impurities adversely affect catalyst activity, stability andefficiency. For example, the scavenging compound will be anorganometallic compound such as the Group 13 organometallic compounds ofU.S. Pat. Nos. 5,153,157; 5,241,025; WO 1991/09882: WO 1994/03506: WO1993/14132; and that of WO 1995/07941. Exemplary compounds includetriethyl aluminum, triethyl borane, tri-iso-butyl aluminum, methylalumoxane, iso-butyl alumoxane, tri-n-octyl aluminum,bis(diisobutylaluminum)oxide, modified methylalumoxane. (Useful modifiedmethylalumoxane include cocatalyst type 3A (commercially available fromAkzo Chemicals, Inc. under the trade name Modified Methylalumoxane type3A) and those described in U.S. Pat. No. 5,041,584). Those scavengingcompounds having bulky or C₆-C₂₀ linear hydrocarbyl substituentsconnected to the metal or metalloid center usually minimize adverseinteraction with the active catalyst. Examples include bulky compoundssuch as triethylaluminum, such as tri-iso-butyl aluminum, such astri-iso-prenyl aluminum, and long-chain linear alkyl-substitutedaluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum,or tri-n-dodecyl aluminum. When alumoxane is used as the activator, anyexcess over that needed for activation will scavenge impurities andadditional scavenging compounds may be unnecessary. Alumoxanes also maybe added in scavenging quantities with other activators, e.g.,methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃(perfluorophenyl=pfp=C₆F₅).

In at least one embodiment, a transfer agent, such as an AVTA, may alsofunction as a scavenger.

In at least one embodiment, two or more catalyst complexes as describedherein are combined with a chain transfer agent, such as TNOAL, in thesame reactor with monomer. Alternately, one or more complexes arecombined with another catalyst (such as a metallocene) and a chaintransfer agent, such as TNOAL, in the same reactor with monomer.

Polymer Products

While the molecular weight of the polymers produced herein is influencedby reactor conditions including temperature, monomer concentration andpressure, the presence of hydrocarbenyl chain transfer agents, chainterminating agents and the like, the branched propylene polymers andcopolymer products produced by the present process may have an Mw ofabout 1,000 g/mol to about 2,000,000 g/mol, alternately of about 30,000g/mol to about 600,000 g/mol, alternately of about 100,000 g/mol toabout 500,000 g/mol, alternately of about 130,000 g/mol to about 400,000g/mol, as determined by Gel Permeation Chromatography. Exemplarypolymers produced herein may be propylene polymers or copolymers. In atleast one embodiment, the comonomer(s) can be present at up to 20 mol %,such as from 0.01 mol % to 15 mol %, such as 1 mol % to 10 mol %. In atleast one embodiment, the comonomer(s) can be present at up to 25 wt %,such as from 0.01 wt % to 25 wt %, such as 1 wt % to 20 wt %, such asfrom 5 wt % to 10 wt %, with the rest being made up of the main monomer,such as propylene.

In a preferred embodiment of the invention, the branched propylenepolymers (such as propylene homo- and/or co-copolymer) produced by thepresent process may have an Mw of about 1,000 g/mol to about 2,000,000g/mol, alternately of about 30,000 g/mol to about 600000 g/mol,alternately of about 100,000 g/mol to about 500,000 g/mol, alternatelyof about 130,000 g/mol to about 400,000 g/mol, as determined by GelPermeation Chromatography; and have comonomer(s) present at from 0 to 20mol %, such as from 0.01 mol % to 15 mol %, such as 1 mol % to 10 mol %,with propylene making up the rest of the copolymer. In at least oneembodiment, the propylene is present at 99.9 to 75 wt %, (preferably99.5 wt % to 75 wt %, preferably 99 wt % to 80 wt %, preferably 95 wt %to 90 wt %) and the comonomer(s) is present at 0.1 to 25 wt %,(preferably 0.5 wt % to 25 wt %, preferably 1 wt % to 20 wt %,preferably 5 wt % to 10 wt %), based upon the weight of the copolymer,and the wt % of the remnant of the metal hydrocarbenyl chain transferagent is excluded.

In a least one embodiment, the branched propylene polymer is 90 wt % orgreater propylene, alternatively 95 wt % or greater propylene,alternatively 98 wt % propylene or greater, alternatively 99 wt %propylene or greater, alternatively 100 wt % propylene wherein the wt %is based on propylene monomer and comonomer(s), and the wt % of theremnant of the metal hydrocarbenyl chain transfer agent is excluded.

In a least one embodiment, the branched propylene polymer is 100 wt %propylene wherein the wt % is based on propylene monomer and the wt % ofthe remnant of the metal hydrocarbenyl chain transfer agent is excluded.

In a preferred embodiment, the branched propylene polymer comprises lessthan 1 wt % ethylene, preferably less than 0.5 wt %/ethylene, preferably0 wt % ethylene.

In a preferred embodiment, the branched propylene polymer comprises lessthan 0.1 wt % diene, preferably less than 0.05 wt % diene, preferably 0wt % diene.

In a preferred embodiment, the branched propylene polymer comprises aremnant of the metal hydrocarbenyl chain transfer agent (preferably from0.001 to 10 mol %, alternatively from 0.01 to 5 mol %, alternatively0.01 to 2 mol %, alternatively 0.01 to 1 mol %).

For purposes of this invention and the claims thereto, when a polymer isreferred to as comprising a metal hydrocarbenyl chain transfer agent,the metal hydrocarbenyl chain transfer agent present in such polymer orcopolymer is the polymerized portion of the metal hydrocarbenyl chaintransfer agent, also referred to as the remnant of the metalhydrocarbenyl chain transfer agent. The remnant of a metal hydrocarbenylchain transfer agent is defined to be the portion of the metalhydrocarbenyl chain transfer agent containing an allyl chain end thatbecomes incorporated into the polymer backbone. For example if the allylchain end of the metal hydrocarbenyl chain transfer agent isCH₂═CH—(CH₂)₆, the “CH₂—CH” carbons of the metal hydrocarbenyl chaintransfer agent become a part of the polymer backbone and the —(CH₂)₆,becomes a part of a side chain.

In at least one embodiment, a polymer is a branched propylene-polymer.Preferred branched propylene polymers herein typically include fromabout 90 wt % to wt % 100% propylene, wherein said branched propylenepolymers have: a) a g′_(vis) of 0.97 or less; b) a strain hardeningratio of 1 or greater; c) an Mw of 50,000 g/mol or more; and d) an Mw/Mnof 4 or less.

In any embodiment described herein, the branched propylene polymer mayhave a) a g′_(vis) of 0.97 or less; b) a strain hardening ratio of 1 orgreater; c) an Mw of 50,000 g/mol or more; and d) an Mw/Mn of 4 or less.

In a preferred embodiment of the invention, the branched propylenepolymers produced by the present process have:

a) an Mw of about 1,000 g/mol to about 2,000,000 g/mol (alternately50,000 g/mol or more, alternately about 30,000 g/mol to about 600,000g/mol, alternately about 100,000 g/mol to about 500,000 g/mol,alternately about 130,000 g/mol to about 400,000 g/mol, as determined byGel Permeation Chromatography);b) comonomer(s) present at 0 to 20 mol % (such as from 0.01 mol % to 15mol %, such as 1 mol % to 10 mol %, with propylene making up the rest ofthe polymer);c) a g′_(vis) of 0.97 or less (preferably 0.95 or less, preferably 0.93or less, preferably 0.90 or less, alternately 0.85 or less, alternately0.80 or less, alternately 0.75 or less, alternately 0.70 or less,alternately 0.60 or less);d) a strain hardening ratio of 1 or greater (preferably such as 5 ormore, alternately 10 or more, alternately 20 or more, alternately 30 ormore, alternately 40 or more, alternately 50 or more); ande) an Mw/Mn of 4 or less (preferably from greater than 1 to 4,preferably from 1.5 to 3).

In any embodiment of the invention described herein, a propylene polymerproduced herein has a g′_(vis) of 0.97 or less (preferably 0.95 or less,preferably 0.93 or less, preferably 0.90 or less, alternately 0.85 orless, alternately 0.80 or less, alternately 0.75 or less, alternately0.70 or less, alternately 0.60 or less).

In any embodiment of the invention described herein, the propylenepolymer has (at 190° C.) one or more of:

-   -   a power law index of from about 0.38 to about 0.63;    -   transition index of from about 0.24 to about 0.52;    -   consistency (characteristic time) of from about 7 s to about 1.5        s;    -   infinite-rate viscosity of from about −181.8 to about −143 Pa·s;        and zero-shear viscosity of from about 117 kPa·s to about 3.9        kPa·s.

In any embodiment of the invention described herein, the propylenepolymer has a shear thinning index at 190° C. of from 1 to 11,preferably from 4 to 7.

In any embodiment of the invention described herein, the propylenepolymer has a terminal unsaturation of 80% or more, based upon thenumber of the total unsaturations.

In any embodiment of the invention described herein, a propylene polymerproduced herein has an MFR (in g/10 min per ASTM D1238 at 230° C./2.16kg test conditions) from 0.1 g/10 min to 100 g/10 min, such as from 1.0g/10 min to 100 g/10 min, such as from 4 g/10 min to 80 g/10 min, suchas from 5 g/10 min to 65 g/10 min, alternately from 3 g/10 min to 70g/10 min.

In any embodiment of the invention described herein, a propylene polymerproduced herein a high-load melt flow rate, HLMFR (in g/10 min per ASTMD1238 at 230° C./21.6 kg test conditions), from 1.0 g/10 min to 100 g/10min, such as from 3.0 g/10 min to 60 g/10 min, such as from 5.0 g/10 minto 50 g/10 min, such as from 10 g/10 min to 30 g/10 min.

In any embodiment of the invention described herein, a propylene polymerproduced herein has an Mw from 100,000 g/mol to 400.000 g/mol, such asfrom 120,000 g/mol to 380,000 g/mol, such as from 140,000 g/mol to360,000 g/mol, such as from 160,000 g/mol to 340,000 g/mol, such as from180,000 g/mol to 320,000 g/mol.

In any embodiment of the invention described herein, a propylene polymerproduced herein an Mn from 20,000 g/mol to 200,000 g/mol, such as from30,000 g/mol to 195,000 g/mol, such as from 40,000 g/mol to 190,000g/mol, such as from 50,000 g/mol to 185,000 g/mol.

In any embodiment of the invention described herein, a propylene polymerproduced herein has an Mw/Mn value from 1.0 to 4, s such as from 1.5 to3.5, such as from 2.0 to 3.0.

In any embodiment of the invention described herein, a propylene polymerproduced herein has a DSC melting point of greater than 100° C., such asgreater than 105° C., such as greater than 110° C., such as greater than115° C. and a DSC melting point of less than 160° C., such as less than145° C., such as less than 130° C., such as less than 120° C.

In any embodiment of the invention described herein, a propylene polymerproduced herein has a DSC peak crystallization temperature, T_(c) (alsoreferred to as crystallization temperature), of greater than 63° C.,such as greater than 64° C., such as greater than 65° C., such asgreater than 66° C. Preferably, a polymer of the present disclosure hasa DSC peak crystallization temperature, T_(c), of 62 to 160° C., such as63 to 145° C., such as 64 to 130° C., such as 65 to 120° C.

In any embodiment of the invention described herein, a propylene polymerproduced herein has a DSC melt enthalpy of greater than 35 J/g, such asgreater than 40 J/g, such as greater than 42 J/g, such as greater than45 J/g. A polymer of the present disclosure can have a DSC melt enthalpyof less than 90 J/g, such as less than 70 J/g, such as less than 60 J/g,such as less than 50 J/g.

In any embodiment of the invention described herein, a propylene polymerproduced herein has a heat of fusion as determined by DSC of greaterthan 35 J/g, such as greater than 40 J/g, such as greater than 42 J/g,such as greater than 45 J/g and preferably less than 90 J/g, such asless than 70 Jig, such as less than 60 J/g, such as less than 50 J/g.

Preferably, the branched propylene polymer produced herein is gel free.Presence of gel can be detected by dissolving the material in xylene atxylene's boiling temperature (140° C.) and measuring the amount of gelpresent (See ASTM D 5492, except that 140° C. is used rather than 20°C.). In any embodiment, the branched propylene polymer has 5 wt % orless (preferably 4 wt % or less, preferably 3 wt % or less, preferably 2wt % or less, preferably 1 wt % or less, preferably 0 wt %) of xyleneinsoluble material.

In any embodiment of the invention described herein, a propylene polymerproduced herein has a unimodal or multimodal molecular weightdistribution as determined by Gel Permeation Chromatography (GPC). By“unimodal” is meant that the GPC trace has one peak or inflection point.By “multimodal” is meant that the GPC trace has at least two peaks orinflection points. An inflection point is that point where the secondderivative of the curve changes in sign (e.g., from negative to positiveor vice versus).

Moments of Molecular weight and other property measurement methods aredescribed in the Experimental Section.

In any embodiment of the invention described herein, a propylene polymerproduced herein has an Mz/Mw from 1 to 10, such as from 2 to 7, such asfrom 2 to 5, such as from 2 to 3. Polymers produced herein have an Mz/Mnfrom 1 to 10, such as from 2 to 6, such as from 3 to 5.

The molecular weight distribution that can be quantified using a ratioof different molecular weight moments (M_(n)—number-average molecularweight, M_(w)—weight-average molecular weight, M_(z)—Z-average molecularweight, etc.) can have a significant effect on the shear-rate/frequencydependence of the steady-shear/complex viscosity (W. Graessley and L.Segal, AlChE., 1970, 16, 261; D. Nicheti and I. Manas-Zloczower, J.Rheol., 1998, 42(4), 951). For example, for samples with similar M_(w),a high M_(w)/M_(n) or M_(z)/M_(w) tends to indicate an earlier onset ofshear thinning behavior with respect to the sample with lowerM_(w)/M_(n) or M_(z)/M_(w) values. Therefore, a polymer with a largerM_(w)/M_(n) or M_(z)/M_(w) ratio would be expected to have a lowerviscosity at high shear rates than a polymer with a similarweight-average molecular weight but a smaller value of M_(w)/M_(n) orM_(z)/M_(w) ratio.

Polymers of the present disclosure can have a high degree of terminalunsaturation, e.g. vinyl end groups. In at least one embodiment, apolymer has a terminal unsaturation of 50% or more of the totalunsaturations, such of 70% or more of the total unsaturations, of 85% ormore of the total unsaturations, of 95% or more of the totalunsaturations. Terminal unsaturation can provide reactive end groups ofpolymers for functionalization.

Unsaturation (internal and terminal) in a polymer can be determined by¹H NMR with reference to Macromolecules, 2014, 47, 3782 andMacromolecules, 2005, 38, 6988, but in event of conflict Macromolecules,2014, 47, 3782 shall control. Peak assignments are determinedreferencing the solvent of tetrachloroethane-1,2 d₂ at 5.98 ppm.Specifically, percent internal unsaturation is determined by addingVy1+Vy2+trisubstituted olefins then dividing by total unsaturation.

The effect of long-chain branching on rheological signal of the sampleswith similar polydispersity of molecular weights can be presented byplotting the phase angle (δ) versus the absolute value of the complexshear modulus (G*) to produce a Van Gurp-Palmen plot (Trinkle S., P.Walter. C. Friedrich, Rheol. Acta 2002, 41, 103). The plot ofconventional polypropylene polymers shows monotonic behavior and anegative slope toward higher G* values. Conventional polypropylenewithout long chain branches tend to exhibit a negative slope on the VanGurp-Palmen plot. The Van Gurp-Palmen plots of some embodiments of thebranched propylene polymers described in the present disclosure exhibittwo slopes—a positive slope at lower G* values and a negative slope athigher G* values.

Useful branched polypropylene polymers used herein have good shearthinning.

Shear thinning is determined by fitting complex viscosity versus radialfrequency curve with Carreau-Yasuda model. Shear thinning can be alsocharacterized using a shear thinning index. Shear thinning ischaracterized by the decrease of the complex viscosity with increasingangular frequency.

The term “shear thinning index” is determined using plots of thelogarithm (base ten) of the complex viscosity versus logarithm (baseten) of the frequency. The slope is the difference in the log (complexviscosity) at a frequency of 100 rad/s and the log (complex viscosity)at a frequency of 0.01 rad's divided by 4. These plots are exemplaryoutput of small amplitude oscillatory shear (SAOS) experiments. Forpurposes of the present disclosure, the SAOS test temperature is 190° C.for propylene polymers and blends thereof. Polymer viscosity isconveniently measured in Pascal*seconds (Pa*s) as function of radialfrequencies within a range of from 0.01 to 628 rad/sec and at 190° C.under a nitrogen atmosphere using a dynamic mechanical spectrometer suchas the TA Instruments Advanced Rheometrics Expansion System (ARES-G2).Generally a low value of shear thinning index indicates that the polymeris highly shear-thinning and that it is readily processable in highshear processes, for example by injection molding. The more negativethis slope, the faster the complex viscosity decreases as the frequencyincreases.

In at least one embodiment, the branched propylene polymers have a shearthinning index at 190° C. of from 1 to 11, such as from 2 to 10, such asfrom 3 to 9, such as from 4 to 7.

Additionally, suitable branched propylene polymers useful herein canhave characteristics of strain hardening in extensional viscosity. Animportant feature that can be obtained from extensional viscositymeasurements is the attribute of strain hardening in the molten state(see, for example, FIG. 1). Strain hardening is observed as a sudden,abrupt upswing of the extensional viscosity in the transient extensionalviscosity vs. time plot. This abrupt upswing, away from the linearviscoelastic behavior, was reported in the 1960s for LDPP and LDPE(reference: J. Meissner, Rheol. Acta., Vol. 8, 78, 1969) and wasattributed to the presence of long branches in the polymer. Thestrain-hardening ratio (SHR) is defined as the ratio of the maximumtransient extensional viscosity at certain strain rate over therespective value of the linear viscoelasticity envelop (LVE) (FIG. 1):SHR({dot over (ε)},t)=η_(E) ⁺({dot over (ε)},t)/3η⁺(t),where linear viscoelasticity envelop η⁺(t) is computed as following:η⁺(t)=Σ_(i=1) ^(N) g _(i)λ_(i)(1−exp(−t/λ _(i))),with parameters g_(i) and λ_(i) obtained by fitting storage and lossmoduli:

${G^{\prime}(\omega)} = {\sum\limits_{i = 1}^{N}{g_{i}\frac{( {\omega\;\lambda_{i}} )^{2}}{1 + ( {\omega\;\lambda_{i}} )^{2}}}}$${G^{''}(\omega)} = {\sum\limits_{i = 1}^{N}{g_{i}{\frac{\omega\;\lambda_{i}}{1 + ( {\omega\;\lambda_{i}} )^{2}}.}}}$Strain hardening is present in the material when the ratio is greaterthan 1. In at least one embodiment, the branched propylene polymers showstrain hardening in extensional flow. For instance, the strain hardeningratio is 2 or greater, such as 5 or greater, such as 10 or greater, suchas 15 or more, when extensional viscosity is measured at a Hencky strainrate of from 0.01 sec⁻¹ to 10 sec⁻¹, such as 1 sec⁻¹, and at atemperature of 190° C.

The branched propylene polymers can also exhibit melt strength valuesgreater than that of conventional linear or long chain branchedpolypropylene of similar melt index. As used herein, “melt strength”refers to the force required to draw a molten polymer extrudate at arate of 12 mm/s² at an extrusion temperature of 190° C. until breakageof the extrudate whereby the force is applied by take up rollers. In atleast one embodiment, the melt strength of the branched modifier polymeris at least 20% higher than that of a linear polypropylene with the samedensity and melt index.

In at least one embodiment, branched propylene polymers produced hereinhave a melt strength of at least about 10 cN, such as at least about 15cN, such as at least about 20 cN, such as at least about 25 cN, such asat least about 30 cN.

In at least one embodiment, the branched propylene polymers have astrain hardening ratio of 1 or more, such as 5 or more, such as 10 ormore, such as 20 or more, such as 30 or more, such as 40 or more, suchas 50 or more.

The shear thinning is described by the following parameters: Power LawIndex (slope of the viscosity vs frequency in the power-law regime),transition index (parameter describing the transition between Newtonianplateau and power law region), consistency (characteristic relaxationtime of the polymer, inverse to the frequency correspondent to thetransition from Newtonian to power-law regime), Infinite-Rate Viscosity,Zero-Shear Viscosity (as defined by fitting dependence of complexviscosity on angular frequency data by Carreau-Yasuda model using TAInstruments Trios v3.3.1.4246 software).

In at least one embodiment, a propylene polymer at 190° C. has:

-   -   a power law index of from about 0.38 to about 0.63;    -   transition index of from about 0.24 to about 0.52;    -   consistency (characteristic time) of from about 7 s to about 1.5        s;    -   infinite-rate viscosity of from about −181.8 to about −143 Pa·s;        and    -   zero-shear viscosity of from about 117 kPa·s, to about 3.9        kPa·s,        as defined by fitting dependence of complex viscosity on angular        frequency data by Carreau-Yasuda model using TA Instruments        Trios v3.3.1.4246 software.

${\frac{{\eta*(\omega)} - \eta_{\infty}}{\eta_{0} - \eta_{\infty}} = \frac{1}{\lbrack {1 + ( {k\;\omega} )^{a}} \rbrack^{{({1 - n})}/a}}},$with η₀ the zero-shear viscosity, η_(∞) the infinite viscosity, k theconsistency and n the power law index and an α parameter describing thetransition between Newtonian plateau and power law region.End Uses

Polymers of the present disclosure may be blended and/or coextruded withany other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, isotacticpolypropylene, ethylene propylene copolymers and the like.

Articles made using polymers produced herein may include, for example,molded articles (such as containers and bottles, e.g., householdcontainers, industrial chemical containers, personal care bottles,medical containers, fuel tanks, and storageware, toys, sheets, pipes,tubing) films, non-wovens, and the like. It should be appreciated thatthe list of applications above is merely exemplary, and is not intendedto be limiting.

In particular, polymers produced by the process of the presentdisclosure and blends thereof are useful in such forming operations asfilm, sheet, and fiber extrusion and co-extrusion as well as blowmolding, injection molding, roto-molding. Films include blown or castfilms formed by coextrusion or by lamination useful as shrink film,cling film, stretch film, sealing film or oriented films.

Experimental

Diisobutylaluminum hydride (DIBAL-H) and triisobutyl aluminum (TIBAL)were purchased from Akzo Nobel and/or Sigma Aldrich and were used asreceived. 1,7-octadiene and 1,9-decadiene were purchased from SigmaAldrich and purified by distillation from sodium metal under a nitrogenatmosphere prior to use. Synthetic procedures involving oxygen reactivespecies, such as organoaluminums and transition metals, were performedunder inert atmosphere using glove box and Schlenk line techniques.Solvents use for the preparation of solutions for NMR spectroscopy weredried over 3 angstrom molecular sieves and sparged with nitrogen priorto use.

Gel Permeation Chromatography with Three Detectors (GPC-3D)

M_(w), M_(n), Mz, and M_(w)/M_(n) are determined by using a HighTemperature Gel Permeation Chromatography (Agilent PL-220), equippedwith three in-line detectors, a differential refractive index detector(DRI), a light scattering (LS) detector, and a viscometer. Experimentaldetails, including detector calibration, are described in: T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, pp. 6812-6820, (2001) and references therein. Three AgilentPLgel 10 micron Mixed-B LS columns are used. The nominal flow rate is0.5 mL/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns, viscometer and differential refractometer (theDRI detector) are contained in an oven maintained at 145° C. Solvent forthe experiment is prepared by dissolving 6 grams of butylatedhydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a0.1 μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the GPC-3D. Polymer solutions are prepared by placingdry polymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous shaking for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.284 g/ml at 145° C. The injectionconcentration is from 0.5 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the viscometer are purged. Flow rate in theapparatus is then increased to 0.5 ml/minute, and the DRI is allowed tostabilize for 8 hours before injecting the first sample. The LS laser isturned on at least 1 to 1.5 hours before running the samples. Theconcentration, c, at each point in the chromatogram is calculated fromthe baseline-subtracted DRI signal, IDRI, using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. Units on parametersthroughout this description of the GPC method are such thatconcentration is expressed in g/cm3, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient. P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

$K_{o} = \frac{4\pi^{2}{n^{2}( {{{dn}/d}\; c} )}^{2}}{\lambda^{4}N_{A}}$where NA is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system, which take the same value as the one obtainedfrom DRI method. The refractive index, n=1.500 for TCB at 145° C. andλ=657 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(s) =c[η]+0.3(c[η])₂where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theGPC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = {\frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}.}$M_(v) is the viscosity-average molecular weight based on molecularweights determined by LS analysis, while a and K are as calculated inthe published in literature (T. Sun, P. Brant, R. R. Chance, and W. W.Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001)),except that for purposes of this invention and claims thereto, α=0.705and K=0.0002288 for propylene polymers. Concentrations are expressed ing/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity(hence K in the Mark-Houwink equation) is expressed in dL/g unlessotherwise noted.

This invention further relates to:

1. A process to produce branched propylene polymers comprising:

1) contacting monomer comprising propylene with a catalyst systemcomprising an activator, a metal hydrocarbenyl chain transfer agent, anda non-metallocene complex; and

2) obtaining a branched propylene polymer comprising from about 90 wt %or greater propylene, wherein said branched propylene polymer: a) has ag′_(vis) of 0.97 or less; b) has strain hardening ratio of 1 or greater;c) has an Mw of 50,000 g/mol or more; and d) has a Mw/Mn of 4 or less.2. The process of paragraph 1, wherein the catalyst compound isrepresented by Formula (I):

wherein:M is a group 3, 4, or 5 metal:J is a three-atom-length bridge between the quinoline and the amidonitrogen;X is an anionic leaving group;L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R², R³, R⁴, R⁵, and R⁶ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyls, halogen, and phosphino:n is 1 or 2;m is 0, 1, or 2n+m is not greater than 4; andany two adjacent R groups may be joined to form a substitutedhydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring,or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8ring atoms and where substitutions on the ring can join to formadditional rings;any two X groups may be joined together to form a dianionic group;any two L groups may be joined together to form a bidentate Lewis base;andan X group may be joined to an L group to form a monoanionic bidentategroup, and wherein the metal hydrocarbenyl chain transfer agent isrepresented by the formula:Al(R′)_(3−v)(R″)_(v)wherein each R′ independently is a C₁-C₃₀ hydrocarbyl group; each R″,independently, is a C₄-C₂₀ hydrocarbenyl group having an end-allylgroup; and v is from 0.1 to 3.3. The process of paragraph 1 or 2, wherein the propylene polymer has(at 190° C.) one or more of:

-   -   a power law index of from about 0.38 to about 0.63;    -   transition index of from about 0.24 to about 0.52;    -   consistency (characteristic time) of from about 7 s to about 1.5        s;    -   infinite-rate viscosity of from about −181.8 to about −143 Pa·s;        and zero-shear viscosity of from about 117 kPa·s to about 3.9        kPa·s.        4. The process of any of paragraphs 1-3, wherein the propylene        polymer has a g′_(vis) of 0.95 or less, preferably 0.90 or less.        5. The process of any of paragraphs 1-4, wherein the propylene        polymer has a Tc of 63° C. or more.        6. The process of any of paragraphs 1-5, wherein the propylene        polymer has a shear thinning index at 190° C. of from 1 to 11.        7. The process of any of paragraphs 1-6, wherein the propylene        polymer has a shear thinning index at 190° C. of from 4 to 7.        8. The process of any of paragraphs 1-7, wherein the propylene        polymer has a terminal unsaturation of 80% or more, based upon        the number of the total unsaturations.        9. The process of any of paragraphs 1-8, wherein the        polymerization is performed in one or more continuous stirred        tank reactors in series or in parallel.        10. The process of paragraph 9, wherein conversion of monomers        is 20% or more.        11. The process of any of paragraphs 1 to 10, wherein the        polymerization is performed at a temperature of from 70° C. to        150° C.        12. The process of paragraph 11, wherein the polymerization is        performed at a temperature of from 80° C. to 120° C.        13. The process of paragraph 12, wherein the polymerization is        performed at a temperature of from 90° C. to 100° C.        14. The process of any of paragraphs 1 to 13, wherein the        catalyst compound has an efficiency greater than 50,000 g        Polymer/g catalyst.        15. The process of any of paragraphs 2 to 14, wherein M is Ti,        Zr, or Hf.        16. The process of any of paragraphs 2 to 15, wherein J is        selected from:

wherein

indicates connection to the catalyst compound.17. The process of paragraph 2, wherein J is dihydro-1H-indenyl and R¹is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.18. The process of paragraph 2, wherein the catalyst compound isrepresented by Formula (II):

wherein M, L, X, m, n, R, R², R³, R⁴, R⁵, R⁶, and R¹³ are as defined inparagraph 1, and E is carbon, silicon, or germanium;R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently selected from hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, or any two adjacent R groups are joined to form a substitutedor unsubstituted hydrocarbyl or heterocyclic ring, wherein the ring has5, 6, 7, or 8 ring atoms and wherein substitutions on the ring can jointo form additional rings.19. The process of paragraph 18, wherein R¹¹ and R¹² are independentlyselected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, andtrimethylsilyl.20. The process of paragraph 18 or 19, wherein E is carbon.21. The process of paragraph 18, wherein R⁷, R⁸, R⁹, and R¹⁰ areindependently selected from hydrogen, methyl, ethyl, propyl, isopropyl,phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, andtrimethylsilyl.22. The process of paragraph 18, wherein R², R³, R⁴, R⁵, and R⁶ areindependently selected from hydrogen, hydrocarbyls, alkoxy, silyl,amino, substituted hydrocarbyls, and halogen.23. The process of paragraph 18, wherein each L is independentlyselected from Et₂O, MeOtBu. Et₃N, PhNMe₂, MePh₂N, tetrahydrofuran, anddimethylsulfide and each X is independently selected from methyl,benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl,hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido,dipropylamido, and diisopropylamido.24. The process of paragraph 18, wherein R¹ is 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl,2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R¹³ isphenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl,2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl,3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.25. The process of paragraph 18, wherein R¹ is 2,6-diisopropylphenyl andR¹ is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbonatoms.26. The process of paragraph 18, wherein the activator comprises analumoxane and or a non-coordinating anion.27. The process of paragraph 26, wherein the activator comprises one ormore of: trimethylammonium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, trimethylammoniumtetrakis(perfluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidiniumdimethylanilinium tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetraphenylborate, and triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, methyldioctadecylammoniumtetrakis(pentafluorophenyl)borate, methyldidodecylammoniumtetrakis(pentafluorophenyl)borate, trihexadecylammoniumtetrakis(pentafluorophenyl)borate.28. The process of any of paragraphs 1 to 27, wherein the metalhydrocarbenyl transfer agent is represented by the formula:Al(R′)_(3−v)(R″)_(v)wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group:each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an allylchain end; andv is from 0.01 to 3.29. The process of paragraph 28, wherein R″ is butenyl, pentenyl,hexenyl, heptenyl, octenyl, decenyl, or dodecenyl, and/or R′ is methyl,ethyl, propyl, isobutyl, or butyl.30. The process of paragraph 28, wherein the metal hydrocarbenyltransfer agent comprises one or more of tri(but-3-en-1-yl)aluminum,tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum,tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum,tri(dodec-11-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum,dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum,dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, anddiisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum,ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum,isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum,methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum,butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, andisobutyl-di(dodec-11-en-1-yl)aluminum.31. A branched propylene polymer comprising propylene and a remnant of ametal hydrocarbenyl chain transfer agent wherein the metal hydrocarbenylchain transfer agent is represented by formula:Al(R′)_(3−v)(R″)_(v)wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each R″,independently, is a C₄-C₂₀ hydrocarbenyl group having an end-vinylgroup; and v is from 0.1 to 3:wherein said branched propylene polymer comprising 90 wt % or morepropylene, wherein said branched propylene polymer: a) has a g′_(vis) of0.97 or less; b) has strain hardening ratio of 1 or greater; c) has anMw of 50,000 g/mol or more; and d) has a Mw/Mn of 4 or less.32. The polymer of paragraph 31, wherein the branched propylene polymerhas 5 wt % or less of xylene insoluble material.33. The polymer of paragraph 31 wherein the propylene polymer has (at190° C.) one or more of:

-   -   a power law index of from about 0.38 to about 0.63;    -   transition index of from about 0.24 to about 0.52;    -   consistency (characteristic time) of from about 7 s to about 1.5        s;    -   infinite-rate viscosity of from about −181.8 to about −143 Pa·s;        and zero-shear viscosity of from about 117 kPa·s to about 3.9        kPa·s.        34. The polymer of paragraph 31, wherein said branched propylene        polymer has a g′_(vis) of less than 0.95.        35. The polymer of paragraph 31, wherein the branched propylene        polymer has a g′_(vis) of 0.90 or less.        36. The polymer of paragraph 31, wherein the branched propylene        polymer has a shear thinning index at 190° C. of from 1 to 11.        37. The polymer of paragraph 31, wherein the branched propylene        polymer has a shear thinning index at 190° C. of from 4 to 7.        38. The polymer of paragraph 31, wherein the branched propylene        polymer comprises 95 wt % or more propylene.        39. The polymer of paragraph 31, wherein the branched propylene        polymer comprises 100 wt % propylene, not including the remnant        of any metal hydrocarbenyl chain transfer agent.        40. The polymer of paragraph 31, wherein the branched propylene        polymer has a terminal unsaturation of 80% or more, based upon        the total unsaturations.

All molecular weights are weight average unless otherwise noted. Allmolecular weights are reported in g/mol unless otherwise noted. Forpurposes of the claims, Mw/Mn is Mw(LS)/Mn(DRI).

Synthesis of AVTA

Preparation of isobutyldi(dec-9-en-1-yl)aluminum (AVTA-2/10),1,9-Decadiene (500 mL, 2.71 mol) was loaded into a round bottomed flask.Diisobutylaluminum hydride (30.2 mL, 0.170 mol) was added dropwise over15 minutes. The mixture was then placed in a metal block maintained at110° C. After 30 minutes the solution had stabilized at a temperature of104° C. The mixture was kept at this temperature for an additional 135minutes at which time ¹H-NMR spectroscopic data indicated that thereaction had progressed to the desired amount. The reaction mixture wascooled to ambient temperature. The excess 1,9-decadiene was removed byvacuum distillation at 44° C./120 mTorr over a 2.5 hours. The productwas further distilled at 50° C./120 mTorr for an additional hour toensure complete removal of all 1,9-decadiene. The isolated product was aclear colorless oil. HNMR spectroscopic data suggests an averageformulation of Al(i-Bu)_(0.9)(decenyl)_(2.1) with an additional ca. 0.2molar equivalent of what is presumed to be the triene formed by theinsertion of 1,9-decadiene into an Al-decenyl bond followed by betahydride elimination. Yield: 70.9 g.

Synthesis of Catalyst Complex QDA-1-Hf-Me₂

Suitable transition metal catalysts of the present disclosure can havehigh rates of olefin propagation and negligible or no chain terminationvia beta hydride elimination, beta methyl elimination, or chain transferto monomer relative to the rate of chain transfer to the AVTA or otherchain transfer agent (CTA) such as an aluminum alkyl if present.Pyridyldiamido and quinolinyldiamido pre-catalysts activated withnon-coordinating activators such as dimethylaniliniumtetrakis(perfluorophenyl)borate and/or dimethylaniliniumtetrakis(perfluoronaphthyl)borate are suitable catalysts for the presentdisclosure. Suitable catalyst compounds included (QDA-1)HfMe₂ (seesynthesis description and polymerization results below). Thequinolinyldiamine ligand2-(8-anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylphenyl)quinolin-8-aminewas prepared as described in US Patent Publication No. 2018/0002352 A1.

Preparation of (QDA-1)HfMe₂. Toluene (80 mL) was added to2-(8-anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylphenyl)quinolin-8-amine(QDA-1 diamine, 5.500 g, 10.46 mmol) and Hf(NMe₂)₄ (3.865 g, 10.89 mmol)to form a clear orange solution after stirring for a few minutes. Themixture was placed on a metal block that was then warmed to 85° C. After21 hours the solution was clear and red tinted. The flask was allowed tocool to near ambient temperature and AlMe₃ (5.279 g, 73.23 mmol) wasadded quickly. The mixture became a darker red. After 7 hours thevolatiles were removed overnight by evaporation with a stream ofnitrogen. The resulting orange solid was crushed with a spatula andtoluene (5 mL) was added to form a slurry. The slurry was stirred for 30minutes then pentane (60 mL) was added. The suspension was stirred for 3hours. The solid was then collected on a frit and washed with coldpentane (2×30 mL) to afford the product as an orange solid. H-NMRspectroscopic data indicated product (QDA-1)HfMe₂ of acceptable purity.Yield: 6.93 g, 90.5%.

POLYMERIZATION EXAMPLES

Polymerizations were carried out in a continuous stirred tank reactorsystem. A I-liter Autoclave reactor was equipped with a stirrer, apressure controller, and a water cooling/steam heating element with atemperature controller. The reactor was operated in liquid fillcondition at a reactor pressure in excess of the bubbling point pressureof the reactant mixture, keeping the reactants in liquid phase.Isohexane and propylene were pumped into the reactors by Pulsa feedpumps. All flow rates of liquid were controlled using Coriolis mass flowcontroller (Quantim series from Brooks). Hydrogen (H₂) flowed as a gasunder its own pressure through a Brooks flow controller. Propylene andhydrogen feeds were combined into one stream and then mixed with apre-chilled isohexane stream that had been cooled to at least 0° C. Themixture was then fed to the reactor through a single line. Theorganoaluminum solution (TNOA and/or AVTA) was also added to thecombined solvent and monomer stream just before it entered the reactorto further reduce any catalyst poisons. Similarly, catalyst solution wasfed to the reactor using an ISCO syringe pump through a separated line.

Isohexane (used as solvent), and propylene were purified over beds ofalumina and molecular sieves. Toluene for preparing catalyst solutionswas purified by the same technique. An isohexane solution of tri-n-octylaluminum (TNOA) (25 wt % in hexane, Sigma Aldrich) was used as scavengersolution. AVTA was diluted in toluene. The pre-catalyst complex(QDA-1)HfMe₂ was activated with N,N-dimethyl anilinium tetrakis(pentafluorophenyl) borate at a molar ratio of about 1:1 in 900 ml oftoluene.

The polymer produced in the reactor exited through a back pressurecontrol valve that reduced the pressure to atmospheric. This caused theunconverted monomers in the solution to flash into a vapor phase whichwas vented from the top of a vapor liquid separator. The liquid phase,comprising mainly polymer and solvent, was collected for polymerrecovery. The collected samples were first air-dried in a hood toevaporate most of the solvent, and then dried in a vacuum oven at atemperature of about 90° C. for about 12 hours. The vacuum oven driedsamples were weighed to obtain yields.

The detailed polymerization process conditions and some characteristicproperties are listed in Table 1. PP-1 was a comparative example madeusing TNOA scavenger and hydrogen chain-terminating agent (and withoutAVTA). For this sample, the scavenger feed rate was adjusted to optimizethe catalyst efficiency, with the feed rate varied from 0 (no TNOA) to15 μmol Al/min. No TNOA was used in the production of samples PP-2through PP-4. The catalyst feed rates may also be adjusted according tothe level of impurities in the system to reach the targeted conversionslisted. All the reactions were carried out at a pressure of about 2.4MPa/g unless otherwise mentioned. Additional processing conditions forthe polymerization process of PP1-PP4, and the properties of thepolymers produced are included below in Table 1.

TABLE 1 Polymerization details and data. PP-1 PP-2 PP-3 PP-4Polymerization 95 95 95 95 temperature (° C.) Catalyst feed rate1.366E−07 1.366E−07 1.821E−07 1.821E−07 (mol Hf/min) Al Additive TNOAAVTA- AVTA- AVTA- 25 wt % 2/10 2/10 2/10 Al feed rate 7.428E−067.722E−05 1.544E−04 1.158E−04 (mol Al/min) Propylene feed 30 30 30 30rate (g/min) Hydrogen (scc/min) 10 0 0 0 Isohexane feed 56.7 54 54 54rate (g/min) Polymer made (g) 473.5 161.2 378.4 367.6 Conversion (wt %39.5 26.9 31.5 30.6 of monomers) Catalyst efficiency 118,375 80,60070,950 68,925 (g polymer/g catalyst) MFR (g/10 min) 4.0 3.2 60.5 20.2Mn_DRI (g/mol) 188,870 125,872 61,290 83,732 Mw_DRI (g/mol) 379,397303,077 145,548 188,374 Mz_DRI (g/mol) 619,362 547,121 278,441 339,584Mn_LS (g/mol) 204,746 142,330 67,557 89,931 Mw_LS (g/mol) 355,381295,174 135,349 182,180 Mz_LS (g/mol) 521,081 509,582 228,369 320,255Mw(LS)/Mn(DRI) 1.88 2.35 2.21 2.18 g′_(vis) 1.06 0.99 0.95 0.95 Tc (°C.) 62.1 66.5 67.2 69.5 Tm (° C.) 110.6 110.6 111.6 111.4 Tg (° C.) −7.5−8.2 −6.0 −6.2 Heat of fusion (J/g) 41.4 41.5 37.2 42.8Differential Scanning Calorimetry (DSC)

Peak melting point, T_(m), (also referred to as melting point), peakcrystallization temperature, T_(c), (also referred to as crystallizationtemperature), glass transition temperature (T_(g)), heat of fusion(ΔH_(f) or H_(f)), and percent crystallinity are determined using thefollowing DSC procedure according to ASTM D3418-03. Differentialscanning calorimetric (DSC) data can be obtained using a TA Instrumentsmodel Q200 machine. Samples weighing approximately 5-10 mg are sealed inanaluminum hermetic sample pan. The DSC data are recorded by firstgradually heating the sample to 200° C. at a rate of 10° C./minute. Thesample is kept at 200° C. for 2 minutes, then cooled to −90° C. at arate of 10° C./minute, followed by an isothermal for 2 minutes andheating to 200° C. at 10° C./minute. Both the first and second cyclethermal events were recorded. Areas under the endothermic peaks weremeasured and used to determine the heat of fusion and the percent ofcrystallinity. The percent crystallinity is calculated using theformula, [area under the melting peak (Joules/gram)/B(Joules/gram)]*100,where B is the heat of fusion for the 100% crystalline homopolymer ofthe major monomer component. These values for B are to be obtained fromthe Polymer Handbook, Fourth Edition, published by John Wiley and Sons,New York 1999, provided; however, a value of 207 J/g is used for theheat of fusion for 100% crystalline polypropylene. The crystallizationtemperatures reported here were obtained during the secondheating/cooling cycle unless otherwise noted.

MFR

The “melt flow rate” (MFR) is measured in accordance with ASTM D 1238 at230° C. and 2.16 kg load. The “high load melt flow rate” (HLMFR) ismeasured in accordance with ASTM D1238 at 230° C. and 21.6 kg load.

Rheology

Complex viscosity is determined as described in the Experimental sectionof U.S. Pat. No. 9,458,310. Also see M. Van Gurp, J. Palmen, Rheol.Bull., 1998, 67, 5-8. The dependence of complex viscosity as a functionof frequency can also be determined from rheological measurements at190° C. The following ratio:[η*(0.1 rad/s)−η*(100 rad/s)]/η*(0.1 rad/s)was used to measure the degree of shear thinning of the polymericmaterials of the embodiments herein, where η*(0.1 rad/s) and η*(100rad/s) are the complex viscosities at frequencies of 0.1 and 100 rads,respectively, measured at 190° C. The higher this ratio, the higher isthe degree of shear thinning.

The transient extensional viscosity was measured using a SER2P TestingPlatform available from Xpansion Instruments LLC, Tallmadge, Ohio, USA.The SER Testing Platform was used on a MCR501 rheometer available fromAnton Paar. The SER Testing Platform is described in U.S. Pat. Nos.6,578,413 and 6,691,569, which are incorporated herein for reference. Ageneral description of transient uniaxial extensional viscositymeasurements is provided, for example, in “Measuring the transientextensional rheology of polyethylene melts using the SER universaltesting platform”, The Society of Rheology, Inc., J. Rheol. 49(3),585-606 (2005), incorporated herein for reference. Strain hardeningoccurs when a polymer is subjected to elongational flow and thetransient extensional viscosity increases with respect to the linearviscoelasticity envelop (LVE). Strain hardening is observed as abruptupswing of the extensional viscosity in the transient extensionalviscosity vs. time plot. A strain hardening ratio (SHR) is used tocharacterize the upswing in extensional viscosity and is defined as theratio of the maximum transient extensional viscosity at certain strainrate over the respective value of the LVE. Strain hardening is presentin the material when the ratio is greater than 1.

For the polymerization results collected in the Table 1, the “PP-1”through “PP-4” labels represent the four propylene polymer samples thatwere produced, T(° C.) is the polymerization temperature which wasmaintained within +/−1° C. “Yield” is mass of polymer sample isolatedafter solvent evaporation and is not corrected for aluminum or catalystresidue mass. Efficiency is reported at grams of polymer per gram of theHf-based pre-catalyst complex, not taking into account the mass of theactivator used.

As shown in Table 1, the samples produced using the AVTA reagents (PP-2through PP-4) demonstrate more long-chain branching relative to the(comparative) sample (PP-1) prepared without AVTA reagent. This is shownby the reduced value of g′_(vis). Additionally, the AVTA producedsamples (PP-2 through PP-4) have molecular weight distributions(Mw(LS)Mn(DRI)) of 2.18 to 2.35, whereas the sample prepared withoutAVTA (PP-1) has a molecular weight distribution of 1.88. The AVTAproduced samples (PP-2 to PP-4) also demonstrate crystallizationtemperatures (Tc) of 67-70° C., whereas the sample produced without AVTA(PP-1) had a Tc of 62° C. The other values measured from thedifferential scanning calorimetry, including enthalpy of fusion, Tm, andTg, show insignificant changes between the inventive and comparativesamples. Additionally, polymer PP-3 was obtained with the highest MFR of61 and with the lowest Mn value of 52,792 g/mol and the lowest Mw valueof 134,819 g/mol. Without being bound by theory, the chosen catalystsystem undergoes alkenyl group transfer with the AVTA, which enables theformation of polymer chains containing end-vinyl groups. Incorporationof these end-vinyl groups into growing polymer chains causes theformation of a long-chain branching in the polypropylene. The resultingpolymer has been shown to have higher melt strength and shear thinningbehavior relative to a linear comparative polymer.

Dynamic Shear Melt

Dynamic shear melt rheological data was measured with an AdvancedRheometrics Expansion System (ARES-G2) from TA Instruments usingparallel plates (diameter=25 mm) in a dynamic mode under nitrogenatmosphere. For all experiments, the rheometer was thermally stable at190° C. for at least 30 minutes before inserting compression-moldedsample of resin onto the parallel plates. To determine the samplesviscoelastic behavior, frequency sweeps in the range from 0.01 to 628rad's were carried out at a temperature of 190° C. under constantstrain. Depending on the molecular weight and temperature, strains inthe linear deformation range verified by strain sweep test were used. Anitrogen stream was circulated through the sample oven to minimize chainextension or cross-linking during the experiments. All the samples werecompression molded at 190° C. A sinusoidal shear strain is applied tothe material if the strain amplitude is sufficiently small the materialbehaves linearly. It can be shown that the resulting steady-state stresswill also oscillate sinusoidally at the same frequency but will beshifted by a phase angle S with respect to the strain wave. The stressleads the strain by δ. For purely elastic materials δ=0° (stress is inphase with strain) and for purely viscous materials, δ=90° (stress leadsthe strain by 90° although the stress is in phase with the strain rate).For viscoelastic materials, 0<δ<90. The shear thinning slope (STS) wasmeasured using plots of the logarithm (base ten) of the complexviscosity versus logarithm (base ten) of the angular frequency. Theslope is the difference in the log(complex viscosity) at a frequency of100 s⁻¹ and the log(complex viscosity) at a frequency of 0.01 s⁻¹divided by 4.

FIG. 1 is a graph illustrating extensional viscosity of linear andbranched homopolypropylenes. PP-2 and PP-4 deviate from linear behavior,indicative of long-chain branching. Without being bound by theory, theextent of long-chain branching suggests that typical chain terminationmechanisms, such as chain transfer to monomer or beta-hydrideelimination to metal, do not readily occur in polymerization conditionsused for the AVTA produced samples (PP-2 to PP-4). Additionally, itindicates that the allyl groups of the AVTA are being incorporated intogrowing polymer chains to form long-chain branches. These othertermination mechanisms would be expected to form linear polymer, such asconventional homopolypropylenes. However, this was not observed with theAVTA polymerizations performed. This observation may be due to thepolymerization temperature of around 95° C., which could maintain aliving polymerization. The level of long-chain branching is expected tobe affected by the overall monomer conversion. The AVTA examples withlong-chain branching were produced with conversions of 27 to 32%. It isexpected that higher levels of branching would occur in equivalent AVTApolymerizations run at higher conversions.

Overall, polypropylene polymers containing long chain branching havebeen obtained by polymerization of propylene using a quinolinyldiamidecatalyst in the presence of aluminum vinyl transfer agent (AVTA).Catalysts of the present disclosure can provide catalyst efficiencygreater than 50,000 gP/gCat and polyolefins, such as propylene polymers,having from about 90 wt % or greater propylene, a g′_(vis) average valueof 0.97 or less, an Mn of 10,000 g/mol or greater, an Mw of 50,000 g/molor greater, and an Mw/Mn of 4 or less.

The phrases, unless otherwise specified, “consists essentially of” and“consisting essentially of” do not exclude the presence of other steps,elements, or materials, whether or not, specifically mentioned in thisspecification, so long as such steps, elements, or materials, do notaffect the basic and novel characteristics of the present disclosure,additionally, they do not exclude impurities and variances normallyassociated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the present disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including.” Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of,” “consisting of,” “selected from thegroup of consisting of,” or “is” preceding the recitation of thecomposition, element, or elements and vice versa.

While the present disclosure has been described with respect to a numberof embodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the present disclosure.

What is claimed is:
 1. A branched propylene polymer comprising propyleneand a remnant of a metal hydrocarbenyl chain transfer agent wherein themetal hydrocarbenyl chain transfer agent is represented by formula:Al(R′)3-v(R″)v wherein each R′, independently, is a C₁-C₃₀ hydrocarbylgroup; each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having anallyl chain end; and v is from 0.1 to 3; wherein said branched propylenepolymer comprises 100 wt % propylene, wherein the wt % is based onpropylene monomer and a wt % of a remnant of the metal hydrocarbyl chaintransfer agent is excluded, wherein said branched propylene polymer: a)has a g′_(vis) of 0.97 or less; b) has strain hardening ratio of 1 orgreater; c) has an Mw of 50,000 g/mol or more; and d) has a Mw/Mn of 4or less.
 2. The polymer of claim 1, wherein the propylene polymer has aTc of 63° C. or more.
 3. The polymer of claim 1, wherein v is from 1.1to
 3. 4. The polymer of claim 3, wherein R″ is butenyl, pentenyl,hexenyl, heptenyl, octenyl, decenyl, or dodecenyl, and/or R′ is methyl,ethyl, propyl, isobutyl, or butyl.
 5. The polymer of claim 1, whereinthe metal hydrocarbenyl transfer agent comprises one or more oftri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, tri(dodec-11-en-1-yl)aluminum,dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum,dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum,diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum,diethyl(dec-9-en-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum,diisobutyl(dec-9-en-1-yl)aluminum, anddiisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum,ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum,isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum,methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum,butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, andisobutyl-di(dodec-11-en-1-yl)aluminum.
 6. The polymer of claim 1,wherein the branched propylene polymer has 5 wt % or less of xyleneinsoluble material.
 7. The polymer of claim 1 wherein the propylenepolymer has (at 190° C.) one or more of: a power law index of from about0.38 to about 0.63; transition index of from about 0.24 to about 0.52;consistency (characteristic time) of from about 7 s to about 1.5 s;infinite-rate viscosity of from about −181.8 to about −143 Pa·s; andzero-shear viscosity of from about 117 kPa·s to about 3.9 kPa·s.
 8. Thepolymer of claim 1, wherein said branched propylene polymer has ag′_(vis) of less than 0.95.
 9. The polymer of claim 1, wherein thebranched propylene polymer has a g′_(vis) of 0.90 or less.
 10. Thepolymer of claim 1, wherein the branched propylene polymer has a shearthinning index at 190° C. of from 1 to
 11. 11. The polymer of claim 1,wherein the branched propylene polymer has a shear thinning index at190° C. of from 4 to
 7. 12. The polymer of claim 1, wherein the branchedpropylene polymer has a terminal unsaturation of 80% or more, based uponthe total unsaturations.
 13. The polymer of claim 1, wherein thepropylene polymer has a g′_(vis) of 0.90 or less.